HEALING SYSTEM FOR CURING A MATERIAL THAT REQUIRES CO2 AS A HEALING REAGENT

专利摘要:
Abstract "Curing systems for carbon dioxide consuming materials" The present invention provides a curing system which is useful for curing carbon dioxide consuming materials as a reagent. The system has a curing chamber containing the material to be cured and a gas containing carbon dioxide. The system includes a device that can supply carbon dioxide to remove ambient air under the system load, which can provide carbon dioxide as it is needed and as it is consumed which can control the concentration of carbon dioxide. carbon, temperature and humidity in the chamber during the curing cycle and which can record and display to a user the variables that occur during the curing process.
公开号:BR112015023238A2
申请号:R112015023238
申请日:2014-03-13
公开日:2020-04-28
发明作者:P Kuppler John；Smith Kenneth；Atakan Vahit；Hu Xudong
申请人:Solidia Technologies Inc；
IPC主号:

专利说明:

“HEALING SYSTEMS FOR MATERIALS CONSUMING CARBON DIOXIDE AND METHOD OF USE THEREOF”
CROSS REFERENCE TO RELATED APPLICATIONS [001] This application claims priority to and benefit from co-pending U.S. provisional patent application Serial No. 61 / 785,226, filed on March 14, 2013, which application is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION [002] The invention generally relates to systems and methods for preparing new composite materials. More particularly, the invention relates to equipment and methods used to manufacture synthetic materials from a variety of commonly available raw materials (or precursors) including water and carbon dioxide. These composite materials are suitable for a variety of uses in construction, infrastructure, art and decoration.
BACKGROUND OF THE INVENTION
CONCRETE MATERIALS AND STONES [003] Human beings have known and used concrete and stone since ancient times. For example, materials such as concrete, slate, granite and marble are used in the construction of several useful structures.
[004] Concrete was used for all types of structures, including highways, buildings and construction components such as pipes, blocks, floors, and sleepers. Concrete has many beneficial properties such as being hard (or resistant to deformation by mechanical forces), fireproof, waterproof, and resistant to elements including resistance to mold growth and fungus growth.
[005] Slate is a fine-grained metamorphic rock composed mainly of quartz and mica (sometimes formulated as KAl2 (AISÍ30io)). Because slate is planar, hard, fireproof, waterproof, and resistant to
2/79 elements including resistance to mold growth and fungus growth, it finds widespread uses in building and construction, such as floor and roof materials. Slate occurs in a variety of colors, for example, gray (light to dark), green, cyan (bluish green) or purple. Slate is generally "laminated", or layered, such that it cleaves to provide distinctive planar surface patterns. Its unique aesthetic and physical qualities have made slate a desirable material in building and construction as well as decorative art and sculpture.
[006] Materials similar to artificial slate have been studied in efforts to replace the most expensive and rare natural slate with easily produced, low-cost mimics. Such efforts, however, still have to produce in a synthetic material that has the desired appearance, texture, density, hardness, porosity and other aesthetic characteristic of the slate although it can be manufactured in large quantities at low cost with minimal environmental impact.
[007] “Composite slate” is the replacement of simulated slate made from recycled rubber and plastic. Although these products resemble slate in appearance and in some properties (mainly that they are waterproof and resist elements), they lack the hardness of the slate, they are not fireproof as the slate is fireproof , and they have a distinctly different “feel”. Up close, they look different. Finally, although they may contain recycled materials, they are based on materials derived from petrochemical products.
[008] Laminated asphalt slabs have an artificial appearance that has made them considerably less desirable than natural slate. Other artificial slate mimics are prepared with a synthetic resin binder. These methods suffer from several deficiencies, including poor reproducibility, low yield, deterioration, high finishing costs,
3/79 unsatisfactory mechanics, and the like.
[009] Granite is an igneous rock comprising mainly quartz, mica and feldspar. It usually has coarse grains within a fine-grained matrix. It is known to occur in nature with varied coloring.
[010] Human beings have known and used granite since ancient times. Its unique aesthetic and physical qualities have made granite a desirable material for building and construction as well as decorative art and sculpture. Materials similar to artificial granite have been studied in efforts to replace the expensive and rare material with easily produced, low-cost mimics. Such efforts, however, still have to produce in a synthetic material that has the desired appearance, texture, density, hardness, porosity and other aesthetic characteristic of granite although it can be manufactured in large quantities at low cost with minimal environmental impact.
[011] Most artificial granite mimics are prepared by combining natural stone powder and minerals with a synthetic resin (eg acrylic, unsaturated polyester, epoxy). These methods suffer from several deficiencies, including poor reproducibility, low yield, deterioration, high finishing costs, unsatisfactory mechanical properties, and the like.
[012] Human beings have known and used marble since ancient times. Its unique aesthetic and physical qualities have made marble a desirable material for building and construction as well as decorative art and sculpture. Materials similar to artificial marble have been studied in efforts to replace the expensive and rare material with easily produced, low-cost mimics. Such efforts, however, still have to produce in a synthetic material that has the desired appearance, texture, density, hardness, porosity and other aesthetic characteristic of marble although it can be manufactured in large quantities at low cost with minimal environmental impact.
4/79 [013] Most mimics of artificial marble are prepared by combining natural stone powder and minerals with a synthetic resin (eg acrylic, unsaturated polyester, epoxy). These methods suffer from several deficiencies, including poor reproducibility, low yield, high finishing costs, deterioration, unsatisfactory mechanical properties, and the like.
CONVENTIONAL CONCRETE CURING CHAMBERS [014] Traditional concrete curing chambers are used in a variety of precast concrete industries. A curing chamber is a volume completely or partially embedded within which a controlled environment can be created. The embedded volume can be defined by the solid walls of a rigid structure such as an enclosure or by a flexible barrier such as a tarpaulin-shaped tarp. After a concrete specimen is formed, it is placed in a controlled environment with sufficient moisture content and a very high temperature to ensure that adequate cure is achieved in reasonable times, typically measured in days. Curing is vital to the quality of concrete products and has a strong influence on properties such as durability, strength and abrasion resistance. Proper curing also helps to alleviate side reactions that occur over time that can cause defects and unwanted color changes in finished products.
[015] Concrete curing helps in the chemical reaction of Portland cement concrete known as hydration. The chamber is intended to keep the controlled environment conditioned and to maintain appropriate humidity within the product for the duration of the curing process. Any notable loss of moisture will significantly delay or prevent hydration and therefore decrease the product's properties. Also, temperature plays a crucial role during the curing process as temperatures below 10C or above 70C are highly unfavorable for curing while a temperature of 60C is ideal.
5/79 [016] Some companies that produce precast concrete try simplified curing processes using large environments or areas covered by tarps that house the products in an attempt to maintain temperature and humidity. These systems can act as a means to maintain the heat generated from the samples as a result of the exothermic reaction that occurs during the hydration reaction or to maintain the heat or humidity that can be provided by external heaters or water spray systems. The most efficient and effective method for curing precast concrete, however, has a permanent, sealed and controllable curing environment.
[017] Several companies exist that specialize in the design, manufacture, and installation of Portland cement concrete curing chambers for the precast industry in the production of a wide range of products included but not limited to paving stones, units concrete masonry (CMLTs), retaining walls, and roof tiles. These curing systems are most often constructed of steel, typically galvanized steel, and are insulated to prevent heat loss and maintain energy efficiency. Some systems are highly automated and include "digital cars" which are automated transfer systems that take the precast products formed from the mold on the shelves of the curing chamber. Commercial curing systems can range from the size of a standard shipping container (approximately 40 ft x 10 ft x 8 ft) at all times to high volume production systems that can be as large as 200 ft x 100 ft x 50 ft. The chambers can be configured as a “Recinto Grande” system if the product is compatible, but for manufacturers with many product lines a “Multiple Path” system is usually used that takes into account the temperature and humidity profile control separate from each individual compartment that can be housed for a different product line.
6/79 [018] FIG. 1 is a schematic diagram of a traditional concrete curing chamber (prior art), including the primary components which are a circulation system, a heat exchanger, and a humidification system. The system may contain one or many blowers for circulating gas that provide very high gas velocities through the products to take into account the distribution of temperature and humidity as needed. The heat exchanger can use a direct gas burner, an indirect gas burner, or an electric heater. The humidification system usually includes spray nozzles or a heated steam generator to supply water vapor to the system. Both temperature and humidity are monitored by sensors that send signals back to a computer or programmable logic controller that is used to control curing parameters. Many systems take into account complete sequenced automation with steps to raise, stop, and cool the temperature and humidity as shown in FIG. 2. FIG. 2 is a graph illustrating a traditional concrete curing profile (prior art) showing temperature as a function of time.
TREATMENT SYSTEMS USING CARBON DIOXIDE [019] Descriptions of systems that use carbon dioxide as a reagent include:
[020] Kraft Energy, which describes its use in various documents such as Kraft Energy Concrete Curing Systems. Kraft Energy on page 195 states that carbonation (of concrete) is “[a] process by which carbon dioxide from air penetrates concrete and reacts with hydroxides, such as calcium hydroxide, to form carbonates. In the reaction with calcium hydroxide, calcium carbonate is formed. ” On page 37, Kraft Energy shows an illustration of a paving stone that has been carbonated. The title under the image states “Typical carbonation found after steam curing a solid block of 7 N / mm2 for 24 hours, (indication
7/79 phenolphthalein). ” The image shows a rectangular block that has a gray region on these surfaces, and a central purple region. It is known that phenolphthalein is a chemical compound with the formula C20H14O4. It becomes colorless in acidic solutions and pink in basic solutions. If the concentration of the indicator is particularly strong, it may appear purple. As is evident from the image, carbonation proceeds only at a shallow depth and does not occur in the central portion of the block.
[021] Also known in the prior art is Murray, Pat. US Γ Ρ 4,117,060, published on Sept. 26, 1978, which is said to disclose a method and apparatus that are provided for the manufacture of concrete or similar construction products, in which a mixture of limestone cementitious binder, such as such as cement, an aggregate, a vinyl copolymer of acetatodibutyl maleate, and a sufficient amount of water to manufacture a relatively dry mixture is compressed into the desired configuration in a mold, and with the mixture being exposed to carbon dioxide gas in the mold, before that compression occurs, such that the carbon dioxide gas reacts with the ingredients to provide a product hardened in an accelerated state of cure having excellent physical properties.
[022] Also known in the prior art is Malinowski, Pat. US Ώ ³⁶ 4,362,679, published on Dec 7, 1982, which is said to disclose a method of molding different types of concrete products without the need to use a curing chamber or an autoclave The concrete subsequent to mixing is molded and externally and / or internally subjected to a vacuum treatment to have it dehydrated and compacted. Then carbon dioxide gas is supplied to the mass while maintaining a sub-pressure in such a way that the gas - as a result of the sub-pressure - diffuses into the capillaries formed in the concrete mass, to quickly harden the mass. In one embodiment (as per the
8/79
FIG. 2) - in which the mass (I) is dehydrated and compacted by means of a mat or plate (2) placed on it and exposed to a sub-pressure through a pipe or a line (5) - the carbon dioxide gas is supplied (via line 6) through said mat or plate (2) while using the sub-pressure prevalent in the mass. In another embodiment (according to FIG. 3), underpressure is applied (via line 5) from one or more sides (2b) of the mold to the interior of the element being molded, by means of special inserts, through holes or cavities within the element or through a layer of porous material (1b) on the inner portion thereof. Then the carbon dioxide gas is supplied correspondingly (via line 6). These two main embodiments can, in certain cases, be combined in different ways. In addition, the concrete can at the same time or subsequently be subjected to another treatment such as impregnation with a suitable solution.
[023] Also known in the prior art is Getson, Pat. US No. ² 4,862,827, published on Sept. 5, 1989, which is said to disclose in column 3, lines 26 to 32, that “Referring to FIG. 1, air inlet 33 and exhaust 37 are shown, with chamber 35 downstream of the air path of air inlet 33. This chamber can be used to introduce carbon dioxide to accelerate and cure certain compositions and / or the same can be used to introduce 30 additional moisture to further accelerate the curing of moisture-curable systems. ” [024] Also known in the prior art is Charlebois, Pat. US N ² 5,800,752, published on Sept. 1, 1998, which is said to disclose composite polymer products, including products made of polymeric concrete, reinforced polymeric concrete and reinforced plastics, as well as most: molding compound, composite sheet molding, mineral molding compound and advanced molding compound systems are produced by the simultaneous application of vibration, heat and pressure to a mixture of filler and polymeric binder. THE
9/79 Simultaneous application of vibration, heat and pressure provides a protective layer of polymerized binder that protects the surfaces of the mold and provides products that are substantially free from cracking, cracking or voids. The process of the present invention substantially reduces the time required to cure polymeric composite products.
[025] Also known in the prior art is Soroushian et al., Pat. US No. ² 5,935,317, published on August 10, 1999, which is said to disclose a pre-curing period for CO2 that is used before the accelerated curing (steam or high pressure steam) of cement and concrete products so a: (1) prepare the products to withstand high temperature and vapor pressure in the accelerated curing environment without microcracking and damage; and (2) incorporate the advantages of carbonation reactions in terms of dimensional stability, chemical stability, increased strength and hardness, and improved abrasion resistance in cement and concrete products without substantially modifying conventional accelerated curing procedures. Depending on the moisture content of the product, the invention can carry out pre-curing by CO2 by first drying the product (for example, at a slightly elevated temperature) and then exposing it to an environment rich in carbon dioxide. Vigorous reactions of cement paste in the presence of carbon dioxide provide products with enhanced chemical and dimensional strength, integrity and stability in a relatively short period of time. Subsequent accelerated curing, even in short periods of time (with less energy consumption and cost) would produce higher performance characteristics than that obtainable with the conventional preset period followed by accelerated curing of cement and concrete products.
[026] Also known in the prior art is Ramme et al., Pat. US No. ² 7,390,444, published on June 24, 2008, which is said to disclose a process for sequestering carbon dioxide from the flue gas emitted from a
10/79 combustion is released. In the process, a foam including a foaming agent and flue gas is formed, and the foam is added to a mixture including a cementitious material (e.g., fly ash) and water to form a foamed mixture. Thereafter, the foamed mixture is allowed to settle, preferably to a controlled low strength material having a compressive strength of 1200 psi or less. The carbon dioxide in the flue gas and residual heat reacts with hydration products in the controlled low resistance material to increase the resistance. In this process, carbon dioxide is sequestered. CLSM can be crushed or pelleted to form a lightweight aggregate with properties similar to the naturally occurring mineral, pumice.
[027] Also known in the prior art is CARBONCURE TECHNOLOGIES INC., Publication of International Patent Application No. ² WO 2012/079173 A1, published on June 21, 2012, which is said to disclose concrete articles, including blocks, substantially planar products (such as floors) and hollow products (such as hollow pipes), which are formed in a mold while carbon dioxide is injected into the concrete in the mold, through perforations.
[028] All of the above documents that describe carbon dioxide reactions with concrete are treating concrete that has Portland cement as a bonding agent. Portland cement cures in the absence of CO2 through a hydration reaction.
[029] In addition, existing methods typically involve energy consumption and large carbon dioxide emissions with an unfavorable carbon footprint.
[030] There is a continuing need for apparatus and methods to manufacture new composite materials that exhibit useful aesthetic and physical characteristics and can be mass produced at low cost with energy consumption
11/79 improved and desirable carbon footprint.
SUMMARY OF THE INVENTION [031] The invention is based in part on the unexpected discovery of new composite materials such as concrete and stone-like materials that can be easily produced from low-cost precursor materials, widely available in particle form by a process suitable for large-scale production. Precursor materials include bonding elements that comprise particulate calcium silicate (for example, ground Volastonite), and particulate filler materials that include minerals (for example, quartz and other materials containing S1O2, granite, mica and feldspar). A fluid component is also provided as a reaction medium, comprising liquid water and / or water vapor and a reagent, carbon dioxide (CO2). Additive materials can include natural or recycled materials, and materials rich in calcium carbonate and materials rich in magnesium carbonate, as well as additives to the fluid component, such as a water-soluble dispersant.
[032] Various additives can be used to adjust the physical appearance and mechanical properties of the resulting composite material, such as particles of colored materials, such as colored glass, colored sand, and colored quartz particles, and pigments (for example, oxide black iron, cobalt oxide and chromium oxide). The term “dyes” can be used to generally refer to either or both colored materials and pigments. In order to simulate a slate-like appearance, particulate fillers can include coarse particles and fine particles. Coarse particles are mainly silicate based materials in order to provide hardness, and fine particles can be a wide variety of materials, including sand, ground, crushed or otherwise fragmented substances selected from minerals and additive materials.
[033] These composite materials can exhibit aesthetic visual patterns
12/79 as well as exhibiting compressive strength, flexural strength and water absorption similar to those of the corresponding natural materials. The composite materials of the invention can be produced using the efficient gas-assisted hydrothermal liquid-phase sintering (HLPS) process at low cost and with much improved energy consumption and carbon footprint. In fact, in preferred embodiments of the invention, CO2 is consumed as a reactive species that results in net CO2 sequestration.
[034] According to one aspect, the invention depicts a curing system for curing a material that requires CO2 as a curing reagent. The material does not cure in the absence of CO2. The material does not consume water as a reagent. The curing system comprises a curing chamber configured to contain a material that consumes CO2 as a reagent (or reagent) and that does not cure in the absence of CO2. The curing chamber has at least one door configured to allow material to be introduced into the curing chamber and removed from the curing chamber, and to have at least one closure for the door, the closure configured to provide an atmospheric seal when closed. in order to prevent contamination of a gas present in the curing chamber by gas outside the curing chamber; a carbon dioxide source configured to supply carbon dioxide gas to the curing chamber via a gas inlet port in the curing chamber, the carbon dioxide source having at least one flow regulation device configured to control a flow rate of carbon dioxide gas in the curing chamber; a gas flow subsystem configured to circulate the gas through the curing chamber for a period of time when the material that consumes CO2 as a chemical reagent is being cured; a temperature control subsystem configured to control a gas temperature inside the chamber; a humidity control subsystem configured to control moisture in the gas inside the chamber to increase or decrease humidity; and at
13/79 minus one controller communicating with at least one of the carbon dioxide source, the gas flow subsystem, the temperature control subsystem, and the humidity control subsystem; and at least one controller configured to independently control over a period of time when the material that consumes CO2 as a chemical reagent is being cured at least a respective unit of the flow rate of the carbon dioxide gas, of the gas circulation through the curing, gas temperature, and humidity in the gas.
[035] In one embodiment, the curing chamber is configured to contain a gas pressure in it that is above atmospheric pressure.
[036] In another embodiment, at least one flow regulation device comprises at least one of a pressure regulator and a flow controller configured to supply carbon dioxide gas at a rate substantially equal to a consumption rate of carbon dioxide by the material that consumes CO2 as a chemical reagent during curing.
[037] In yet another embodiment, at least one flow regulating device comprises at least one of a pressure regulator and a flow controller configured to supply carbon dioxide gas at a rate sufficient to purge the ambient atmosphere. of the curing chamber in a period between 2 and 120 minutes to obtain a target CO2 concentration in a range of 50 to 90% by volume.
[038] In yet another embodiment, at least one flow regulating device comprises at least one of a pressure regulator and a flow controller configured to deliver carbon dioxide gas at a rate substantially equal to a rate of venting the curing chamber gas.
[039] In another embodiment, the gas flow subsystem includes a measuring device configured to measure an amount of carbon dioxide in the gas present in the curing chamber.
14/79 [040] In one embodiment, the gas flow subsystem includes a measuring device configured to measure a gas velocity of the gas present in the curing chamber.
[041] In one embodiment, the measuring device configured to measure a gas velocity is one selected from a pilot tube, an orifice plate, an anemometer and a laser Doppler detection system.
[042] In one embodiment, the gas flow subsystem includes a variable speed blower configured to circulate the gas at a desired speed in the curing chamber.
[043] In yet another embodiment, the temperature control subsystem includes a temperature sensor configured to measure the temperature of the gas in the curing chamber.
[044] In an additional embodiment, the temperature control subsystem includes a heat exchanger to regulate the temperature of the gas in the curing chamber.
[045] In an additional embodiment, the temperature control subsystem includes a heat exchanger to control a temperature of the carbon dioxide gas supplied to the curing chamber via the gas inlet port in the curing chamber.
[046] In yet another embodiment, the temperature control subsystem includes a heater located on an external surface of the curing chamber or built into the chamber walls.
[047] In one embodiment, the humidity control subsystem includes a measuring device configured to determine a relative humidity of the gas inside the chamber.
[048] In another embodiment, the humidity control subsystem includes a condenser and one-way condensate water drain
15/79 configured to reduce the humidity in the gas inside the chamber.
[049] In yet another embodiment, the humidity control subsystem includes an exhaust valve configured to reduce the humidity in the gas inside the chamber.
[050] In yet another embodiment, the humidity control subsystem includes a water supply configured to increase the humidity in the gas inside the chamber.
[051] In another embodiment, the at least one controller is a programmable logic controller.
[052] In yet another embodiment, the at least one controller is a general purpose programmable computer that operates under the control of a set of instructions recorded in a machine-readable medium.
[053] In an additional embodiment, the at least one controller includes a screen configured to display to a user any of the duration of a curing cycle, the flow rate of carbon dioxide gas, a concentration of carbon dioxide carbon in the curing chamber, a pressure of the gas in the curing chamber, a rate of circulation of the gas through the curing chamber, the temperature of the gas, and the humidity in the gas.
[054] In an additional embodiment, the at least one controller is configured to record any one of the duration of a curing cycle, the flow rate of carbon dioxide gas, a concentration of carbon dioxide in the curing chamber , a pressure of the gas in the curing chamber, a rate of circulation of the gas through the curing chamber, the temperature of the gas, and the humidity in the gas.
[055] In yet another embodiment, the at least one controller includes a touchscreen.
BRIEF DESCRIPTION OF THE DRAWINGS [056] FIG. 1 is a schematic diagram of a
16/79 traditional concrete (prior art).
[057] FIG. 2 is a graph illustrating a traditional concrete curing profile (prior art) showing temperature as a function of time.
[058] FIGS. 3 (a) to 3 (c) are schematic illustrations of cross sections of connecting elements according to exemplary embodiments of the present invention, including three exemplary core morphologies: (a) fibrous, (b) elliptical, and (c ) with equal axes.
[059] FIGS. 4 (a) to 4 (f) are schematic illustrations of the side view and cross-sectional views of composite materials according to exemplary embodiments of the present invention, illustrating (a) 1D oriented fiber-shaped connecting elements in a matrix diluted connection elements (connection elements are not touching), (b) 2D oriented plate-shaped connection elements in a diluted connection matrix (connection elements are not touching), (c) oriented plate-shaped connection elements 3D in a diluted bonding matrix (bonding elements are not touching), and (d) platelet-shaped connecting elements randomly oriented in a diluted bonding matrix (connecting elements are not touching), in which composite materials include the bonding matrix and filler components such as polymers, metals, inorganic particles, aggregates etc., (e) a concentrated bonding matrix (with a fraction in volume sufficient to establish a loss network) connection elements where the matrix is oriented 3D, and (f) a concentrated connection matrix (with a fraction in volume sufficient to establish a percolation network) of randomly oriented connection elements, in which filler components such as polymers , metals, inorganic particles, aggregates, etc. can be included.
[060] FIG. 5 is a schematic diagram of a concrete CO2 curing chamber constructed and operated in accordance with the principles of the invention.
17/79 [061] FIG. 6 is a schematic diagram of a concrete CO2 curing chamber that provides humidification according to the principles of the invention.
[062] FIG. 7 is a schematic diagram of a CO2 curing chamber that provides dehumidification by purging wet gas according to the principles of the invention.
[063] FIG. 8 is a schematic diagram of a CO2 curing chamber that provides dehumidification using a cooled heat exchanger according to the principles of the invention.
[064] FIG. 9 is a schematic diagram of a curing chamber that has a CO2 purge line and a constant flow CO2 refill line according to the principles of the invention.
[065] FIG. 10 is a schematic diagram of a curing chamber that has a CO2 purge line and that can provide pressure-regulated CO2 replenishment according to the principles of the invention.
[066] FIG. 11 is a schematic diagram of a medium-sized curing chamber with multiple moisture control methods as well as the ability to control and replenish CO2 using constant flow or pressure regulation and which can control moisture according to the principles of the invention.
[067] FIG. 12 is an image of several drum reactors built from 55 gallon (208.19 L) stainless steel drums.
[068] FIG. 13 is an image of the interior of a drum reactor including shelves to support reeds of materials to be processed therein.
[069] FIG. 14 is an image of the exterior of a drum reactor surrounded by a heating jacket, and showing several thermocouple connectors and a gas inlet port.
[070] FIG. 15 is an image of a control panel for a
18/79 drum showing four controllers that control (from left to right) an immersion heater, a liner heater, an in-line gas heater, and a fan, with readings for the temperatures of the three heaters.
[071] FIG. 16 is an image of a commercially available concrete curing chamber built by CDS Inc. that has been retrofitted for low pressure CO2 curing according to the principles of the invention.
[072] FIG. 17 is an image of a portion of the interior of the chamber of FIG. 16, which shows other modifications made to the Portland cement curing system of the prior art.
[073] FIG. 18 is another view of the 1740 CO2 NDIR analyzer.
[074] FIG. 19 is a view inside the curing chamber that illustrates additional components that have been added.
[075] FIG. 20 is a screen capture of the monitor connected to a programmable logic controller that controls a curing chamber according to the principles of the invention.
[076] FIG. 21 is the corresponding temperature and humidity profile for example 5.
[077] FIG 22 is the corresponding temperature and humidity profile for example 6.
DETAILED DESCRIPTION OF THE INVENTION [078] The essence of this invention is a curing system that generates a controlled atmosphere through which temperature, pressure, CO2 concentration, relative humidity and gas velocity are monitored and controlled to generate final products based on concrete that will predominantly cure in the presence of CO2 and will not cure completely in the absence of CO2.
Composite materials manufactured by hydrothermal liquid-phase sintering [079] This invention provides apparatus and methods used to manufacture new
19/79 composite materials that are cured predominantly by a CO2 consumption reaction, which exhibit useful properties and can be easily produced from low-cost precursor materials, widely available by a process suitable for large-scale production with minimal environmental impact . Precursor materials include materials rich in cheap and abundant calcium silicate and calcium carbonate, for example, ground Volastonite, ground limestone, coarse particles and fine particles. Coarse particles and fine particles are mainly S1O2 based materials in order to provide hardness. Coarse and fine particles can include minerals (for example, quartz and other materials that carry S1O2, granite, mica and feldspar). Other key process components include water and CO2. Various additives can be used to modify and adjust the physical appearance and / or mechanical properties of the resulting composite material, such as using pigments (for example, black iron oxide, cobalt oxide and chromium oxide) and colored glass and / or quartz colorful.
[080] These composite materials exhibit various patterns, textures and other characteristics, such as visual patterns of various colors. In addition, the composite materials of the invention exhibit properties of compressive strength, flexural strength and water absorption similar to conventional concrete or the corresponding natural materials. In addition, composite materials can be produced, as disclosed here, using the energy efficient HLPS process and can be manufactured at low cost and with a favorable environmental impact. For example in preferred embodiments of the invention, CO2 is used as a reactive species that results in the sequestration of CO2 in composite materials produced with a carbon footprint unmatched by any existing production technology. The HLPS process is thermodynamically driven by the free energy of the chemical reaction (s) and reduced energy on the surface (area) caused by crystal growth. The kinetics of the HLPS process proceed in
20/79 a reasonable rate at low temperature because a solution (aqueous or non-aqueous) is used to transport the reactive species instead of using a medium or high melting medium fluid in a solid state by temperature.
[081] Debates on various aspects of HLPS can be found in US Patent No. ² 8,114,367, Pub. US N ² US 2009/0143211 (Serial Order No. ² 12 / 271,566), Pub. US N ² US 2011/0104469 ( Serial Order No. ² 12 / 984.299), Pub. US No. ² 20090142578 (Serial Order No. ² 12 / 271.513), WO 2009/102360 (PCT / US2008 / 083606), WO 2011/053598 (PCT / US2010 / 054146), WO 2011/090967 (PCT / US2011 / 021623), US Serial Application N ² 13 / 411,218 filed on March 2, 2012 (Riman et al.), US Serial Application N ² 13 / 491,098 filed on June 7, 2012 (Riman et al), Provisional US Patent Application No. ² 61 / 708,423 filed on October 1, 2012, and US Provisional Patent Application No. ²² 61 / 709,435, 61 / 709,453, 61 / 709,461, and 61 / 709,476, all filed on October 4, 2012, each of which is expressly incorporated herein by reference in its entirety for all purposes.
[082] In certain embodiments, the composite further includes a pigment. The pigment can be uniformly dispersed or substantially non-uniformly dispersed in the bonding matrices, depending on the desired composite material. The pigment can be any suitable pigment including, for example, oxides of various metals (for example, iron oxide, cobalt oxide, chromium oxide). The pigment can be of any color or colors, for example, selected from black, white, blue, gray, pink, green, red, yellow and brown. The pigment can be present in any suitable amount depending on the desired composite material, for example in an amount ranging from about 0.0% to about 10% by weight (for example, about 0.0% to about 8% , about 0.0% to about 6%, about 0.0% to about 5%, about 0.0% to about 4%, about 0.0% to about 3%, about from 0.0% to
21/79 about 2%, about 0.0% to about 1%, about 0.0% to about 0.5%, about 0.0% to about 0.3%, about 0.0% to about 2%, about 0.0% to about 0.1%).
[083] The plurality of connecting elements can have any suitable median particle size and size distribution depending on the desired composite material. In certain embodiments, the plurality of connecting elements have a median particle size in the range of about 5 pm to about 100 pm (e.g., about 5 pm to about 80 pm, about 5 pm to about from 60 pm, about 5 pm to about 50 pm, about 5 pm to about 40 pm, about 5 pm to about 30 pm, about 5 pm to about 20 pm, about 5 pm to about from 10 pm, about 10 pm to about 80 pm, about 10 pm to about 70 pm, about 10 pm to about 60 pm, about 10 pm to about 50 pm, about 10 pm to about from 40 pm, about 10 pm to about 30 pm, about 10 pm to about 20 pm).
[084] The plurality of filler particles can have any suitable median particle size and size distribution. In certain embodiments, the plurality of filler particles has a median particle size in the range of about 5 pm to about 7 mm (for example, about 5 pm to about 5 mm, about 5 pm to about 4 mm, about 5 pm to about 3 mm, about 5 pm to about 2 mm, about 5 pm to about 1 mm, about 5 pm to about 500 pm, about 5 pm to about 300 pm, about 20 pm to about 5 mm, about 20 pm to about 4 mm, about 20 pm to about 3 mm, about 20 pm to about 2 mm, about 20 pm to about 1 mm, about 20 pm to about 500 pm, about 20 pm to about 300 pm, about 100 pm to about 5 mm, about 100 pm to about 4 mm, about 100 pm to about 3 mm, about 100 pm to about 2 mm, about 100 pm to about 1 mm).
[085] In certain preferred embodiments, the filler particles are made of a material rich in calcium carbonate such as limestone
22/79 (for example, ground limestone). In certain materials, the filler particles are made of one or more material based on SiO2 or based on silicate such as quartz, mica, granite, and feldspar (for example, ground quartz, ground mica, ground granite, ground feldspar) .
[086] In certain embodiments, filler particles may include natural, synthetic and recycled materials such as glass, recycled glass, coal slag, material rich in calcium carbonate and material rich in magnesium carbonate.
[087] The plurality of linkers can be chemically transformed from any suitable precursor materials, for example, from a precursor calcium silicate except volastonite. The precursor calcium silicate can include one or more chemical elements of aluminum, magnesium and iron.
[088] As used here, the term "calcium silicate" refers to naturally occurring minerals or synthetic materials that are comprised of one or more of a group of calcium-silicon containing compounds including CaSiOa (also known as "Volastonite" or “pseudo-volastonite” and sometimes formulated as CaOSiCk), Ca3SÍ2O (also known as “Ranquinite” and sometimes formulated as 3CaO2Si02), Ca2SiCU (also known as “Belita” and sometimes formulated as 2CaOSi02), CaaSiOs (also known as “Alita” and sometimes formulated as SCaOSiCte), material that may include one or more other metal ions and oxides (for example, aluminum, magnesium, iron or manganese oxides), or combinations thereof, or may include a naturally occurring amount of magnesium silicate in form (s) or synthetic (s) ranging from trace amount (1%) to about 50% or more by weight.
[089] It should be understood that compositions and methods disclosed here can be adopted to use magnesium silicate in place of or in addition to silicate
23/79 calcium. As used here, the term "magnesium silicate" refers to naturally occurring minerals or synthetic materials that are comprised of one or more of a group of compounds containing magnesium-silicon including, for example, Mg2SiCU (also known as "Fosterite ”) And Mg3SÍ40io (OH) 2) (also known as“ Talc ”), which material may include one or more other metal tenses and oxides (for example, calcium, aluminum, iron or manganese oxides), or combinations thereof, or they may include an amount of calcium silicate in naturally occurring or synthetic form (s) ranging from trace amount (1%) to about 50% or more by weight.
[090] The term “quartz”, as used here, refers to any material based on S1O2, including common sands (construction and masonry), as well as glass and recycled glass. The term also includes any other recycled natural and synthetic materials that contain significant amounts of S1O2 (for example, mica sometimes formulated as KAl2 (AISIS30)).
[091] The weight ratio of (connecting elements): (filler particles) can be any suitable ratios depending on the desired composite material, for example, in the range of about (15 to 50): about (50 to 85) .
[092] In certain preferred embodiments, the plurality of bonding elements is prepared by chemical transformation of the ground Volastonite (or a precursor calcium silicate other than volastonite or magnesium silicate) by reacting it with CO2 through a process of Gas-assisted HLPS.
[093] In certain embodiments, the composite material is characterized by a compressive strength of about 90 MPa to about 175 MPa (for example, about 90 MPa to about 150 MPa, about 90 MPa to about 140
MPa, about 90 MPa to about 130 MPa, about 90 MPa to about 120 MPa, about 90 MPa to about 110 MPa, about 100 MPa to about 175 MPa, about 120 MPa to about 175 MPa, about 130 MPa to about 175 MPa, about
24/79
140 MPa to about 175 MPa, about 150 MPa to about 175 MPa, about 160 MPa to about 175 MPa).
[094] In certain embodiments, the composite material is characterized by a flexural strength of about 5 MPa to about 30 MPa (for example, about 5 MPa to about 25 MPa, about 5 MPa to about 20 MPa, about 5 MPa to about 15 MPa, about 5 MPa to about 10 MPa, about 10 MPa to about 30 MPa, about 20 MPa to about 30 MPa, about 25 MPa to about 30 MPa).
[095] In certain embodiments, the composite material is characterized by water absorption of less than about 10% (for example, less than about 8%, 5%, 4%, 3%, 2%, 1 %).
[096] In certain embodiments, the composite material has less than about 10% by weight of one or more minerals selected from quartz, mica, feldspar, calcium carbonate and magnesium carbonate.
[097] The composite material can exhibit any desired textures, patterns and physical properties, in particular those that are characteristic of natural stone. In certain preferred embodiments, the composite material exhibits a visual pattern similar to natural stone. Other features include colors (for example, black, white, blue, pink, gray (light to dark), green, red, yellow, brown, cyan (bluish green) or purple) and textures.
[098] In another aspect, the invention generally relates to a process for preparing a composite material. The process includes: mixing a particulate composition and a liquid composition to create a slurry mixture; form the slurry mixture into a desired shape, molding the slurry into a mold, pressing the slurry into a mold, pressing the slurry into a vibrating mold, extruding the slurry, forming sliding form the slurry, or using any other form forming method
25/79 common in concrete production; and curing the slurry mixture formed at a temperature in the range of about 20 ° C to about 150 ° C for about 1 hour to about 80 hours under a steam comprising water and CO2 and having a pressure in the range from about ambient atmospheric pressure to about 50 psi above ambient atmospheric pressure and having a CO2 concentration ranging from about 10% to about 90% to produce a composite material exhibiting a texture and / or pattern.
[099] The particulate composition includes a ground calcium silicate having a median particle size in the range of about 1 pm to about 100 pm, and a ground calcium carbonate or a S1O2 bearing material having a median particle size in range from about 3 pm to about 7 mm. The liquid composition includes water and a water-soluble dispersant.
[0100] In certain embodiments, the particulate composition further includes a second ground calcium carbonate having substantially smaller or larger median particle size than the first ground limestone. The process may further include, before curing the molten mixture, the step of drying the molten mixture. The particulate composition further comprises a pigment or dye as discussed herein.
[0101] In certain embodiments, curing the formed slurry mixture is carried out at a temperature in the range of about 30 ° C to about 120 ° C for about 1 hour to about 70 hours under a steam comprising water and CO2 and having a pressure in the range of about ambient atmospheric pressure to about 30 psi above ambient atmospheric pressure.
[0102] In certain embodiments, curing the formed slurry mixture is carried out at a temperature in the range of about 60 ° C to about 110 ° C for about 1 hour to about 70 hours under a steam comprising water and CO2 and having a pressure in the range of about ambient atmospheric pressure at
26/79 about 30 psi above ambient atmospheric pressure.
[0103] In certain embodiments, curing the formed slurry mixture is carried out at a temperature in the range of about 80 ° C to about 100 ° C for about 1 hour to about 60 hours under a steam comprising water and CO2 and having a pressure in the range of about ambient atmospheric pressure to about 30 psi above ambient atmospheric pressure.
[0104] In certain embodiments, curing the formed slurry mixture is carried out at a temperature equal to or lower than about 60 ° C for about 1 to about 50 hours under a steam comprising water and CO2 and having an ambient atmospheric pressure.
[0105] In certain embodiments, the ground calcium silicate includes mainly ground Volastonite, the first ground calcium carbonate includes mainly a first ground limestone, and the second ground calcium carbonate includes mainly a second ground limestone.
[0106] For example, in some embodiments, ground Volastonite has a median particle size of about 5 pm to about 50 pm (for example, about 5 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 40 pm, 90 pm), an apparent density of about 0.6 g / ml to about 0.8 g / ml (loose) and about 1.0 g / ml to about 1, 2 g / mL (penetrated), a surface area of about 1.5 m ² / g to about 2.0 m ² / g. The first ground S1O2 bearing material has a median particle size of about 40 pm to about 90 pm (for example, about 40 pm, 50 pm, 60 pm, 70 pm, 80 pm, 30 pm, 90 pm) , an apparent density of about 0.7 g / ml to about 0.9 g / ml (loose) and about 1.3 g / ml to about 1.6 g / ml (penetrated).
[0107] In certain preferred embodiments, the liquid composition includes water and a water-soluble dispersant comprising a polymeric salt (for example, an acrylic homopolymer salt) having a concentration of about 0.1
27/79% to about 2% w / w of the liquid composition.
[0108] In yet another aspect, the invention generally relates to a composite material prepared according to a process disclosed here, for example, a composite material having a compressive strength of about 90 MPa to about 175 MPa and a flexural strength of about 5.4 MPa to about 20.6 MPa.
[0109] In yet another aspect, the invention generally relates to an article of manufacture manufactured from a composite material disclosed herein.
[0110] Any suitable precursor materials can be used. For example, calcium silicate particles formed mainly from Volastonite, CaSiOa, can react with carbon dioxide dissolved in water. Calcium cations are believed to be leached from Volastonite and transform the peripheral portion of the Volastonite nucleus into calcium-deficient Volastonite. As calcium cations continue to be leached from the peripheral portion of the nucleus, the structure of the peripheral portion eventually becomes unstable and breaks, thereby transforming the peripheral portion of the core's calcium-deficient Volastonite into a predominantly silica-rich first layer. However, a second layer predominantly of calcium carbonate precipitates from the water.
[0111] More specifically, the first layer and the second layer can be formed from the precursor particle according to the following reaction (1):
CaSiOa (s) + CO2 (g) = CaCOa (s) + S1O2 (s) AH ^Q = -87 kJ / mol CO2 (1)
For example, in a silicate mineral carbonation reaction such as with Volastonite, CO2 is introduced as a gas phase that dissolves in an infiltration fluid, such as water. The dissolution of CO2 forms a kind of carbonic acid that results in a decrease in pH in solution. The weakly acid solution incongruently dissolves the CaSiOa calcium species. The released calcium cations and the dissociated carbonate species lead to the precipitation of
28/79 insoluble carbonates. Layers rich in silica are considered to remain in the mineral particles as suppressed layers of calcium.
[0112] Thus, according to a preferred embodiment of the invention, CO2 preferably reacts with the calcium cations of the precursor core of Volastonite, thereby transforming the peripheral portion of the precursor core into a first layer rich in silica and a second layer rich in calcium carbonate. Also, the presence of the first and second layers in the core acts as a barrier for further reaction between Volastonite and carbon dioxide, resulting in the connecting element having the core, first layer and second layer.
[0113] In some embodiments, silicate materials having metals except Ca or in addition to Ca, for example Fosterite (Mg2SiO4), Diopside (CaMgSi2Oe), and Talc (Mg3SÍ40io (OH) 2) can react with carbon dioxide dissolved in water in a manner similar to the Volastonite reaction, as described above. It is believed that such silicate materials can be used, alone, in combination, and / or in combination with Volastonite, as precursors for bonding elements according to the principles of the invention.
[0114] Preferably, gas-assisted HLPS processes utilize partially infiltrated pore space to allow gas diffusion to rapidly infiltrate the porous preform and saturate thin films of liquid interfacial solvent in the pores with dissolved CO2. CO2-based species have low solubility in pure water (1.5 g / L at 25 ° C, 1 atm.). Thus, a substantial amount of CO2 must be continuously supplied to and distributed throughout the porous preform to allow significant carbonate conversion. Using gas phase diffusion offers a considerable increase (about 100 times) in the diffusion length over that of diffusing soluble CO2 an equivalent time in a liquid phase. (“Handbook of chemistry and physics”, Editor: DR Lide, Chapters 6 and 8, 87 ^to
29/79
2006-2007 Edition, CRC.) This partially infiltrated state allows the reaction to proceed to a high degree of carbonation over a fixed period of time.
[0115] Liquid water in the pores accelerates the reaction rate because it is essential for ionization of both carbonic acid and calcium species. However, water levels need to be low enough that CO2 gas can diffuse into the porous matrix before dissolving in the aqueous phase attached to the pore. In addition, the actively dissolving porous preform serves as a standard for expansive reactive crystal growth. Thus, the connecting element and matrices can be formed with minimal distortion and residual stress. This allows large and complex shapes to result, such as those needed for infrastructure and building materials, in addition to many other applications.
[0116] Thus, various combinations of curing conditions can be planned to achieve the desired production process, including varying reaction temperatures, pressures and reaction lengths. In a first exemplary embodiment, water is released to the precursor materials in liquid form with CO2 dissolved in it and the curing process is conducted at about 90 ° C and about 20 psig (ie, 20 psi above ambient pressure) for about 48 hours. In a second exemplary embodiment, water is present in the precursor material (for example, as residual water from the previous mixing step) and water vapor is supplied to the precursor materials (for example, to maintain the water level and / or prevent water loss from evaporation) together with CO2 and the curing process is carried out at about 60 ° C and 0 psig (at ambient atmospheric pressure) for about 19 hours. In a third exemplary embodiment, water is released to the precursor materials in the form of steam together with CO2 and the curing process is carried out at about 90 ° C and 20 psig (20 psi above ambient atmospheric pressure) for about 19 hours.
[0117] In yet another aspect, the invention generally relates to a
30/79 composite material which includes: a plurality of connecting elements and a plurality of filler particles. Each connecting element includes: a core comprising mainly magnesium silicate, a primary or inner layer rich in silica, and a secondary or outer layer rich in magnesium carbonate. The plurality of bonding elements and the plurality of filler particles together form one or more bonding matrices and the bonding elements and the filler particles are substantially uniformly dispersed in them and bonded together, whereby the composite material exhibits one or more textures, patterns and physical properties.
[0118] Compositions and methods disclosed here in relation to calcium silicate can be adopted to use magnesium silicate in place of or in addition to calcium silicate.
B. CONNECTION ELEMENTS, CONNECTION MATRIXES AND COMPOSITE MATERIALS
B1. CONNECTION ELEMENTS [0119] As schematically illustrated in FIGs. 3 (a) to 3 (c), a connecting element includes a core (represented by the black inner portion), a first layer (represented by the white intermediate portion) and a secondary or encapsulating layer (represented by the outer portion). The first layer can include only one layer or multiple sublayers and can completely or partially cover the core. The first layer can exist in a crystalline phase, an amorphous phase or a mixture of these, and can be in a continuous phase or as separate particles. The second layer can include only one layer or multiple sublayers and can also cover the first layer completely or partially. The second layer can include a plurality of particles or it can be a continuous phase, with minimal separate particles.
[0120] A connecting element can display any size and any
31/79 regular or irregular, solid or hollow morphology depending on the intended application. Exemplary morphologies include: cubes, cuboids, prisms, discs, pyramids, polyhedra or many-sided particles, cylinders, sphere, cones, rings, tubes, bows, needles, fibers, filaments, flakes, sphere, subsphere, pearls, grapes, granular , oblong, poles, waves, etc.
[0121] In general, as discussed in more detail here, a linker is produced from reactive precursor materials (eg, precursor particles) through a transformation process. The precursor particles can be of any size and shape as long as they satisfy the needs of the intended application. The transformation process generally leads to the corresponding connecting elements having similar sizes and shapes of the precursor particles.
[0122] Precursor particles can be selected from any suitable material that can undergo suitable transformation to form the desired bonding elements. For example, precursor particles can include oxides and non-oxides of silicon, titanium, aluminum, phosphorus, vanadium, tungsten, molybdenum, gallium, manganese, zirconium, germanium, copper, niobium, cobalt, lead, iron, indium, arsenic, tantalum, and / or alkaline earth elements (beryllium, magnesium, calcium, strontium, barium and radium).
[0123] Exemplary precursor materials include oxides such as silicates, titanates, aluminates, phosphates, vanadates, tungstates, molybdates, gates, manganates, zirconates, germinates, cuprates, stannates, hafinates, chromates, niobates, cobaltates, plumbates, ferrites arsenates, tantalates and combinations of these. In some embodiments, the precursor particles include silicates such as orthosilicates, serosilicates, cyclosilicates, inosilicates, phyllosilicates, tectosilicates and / or hydrated calcium silicate.
[0124] Certain waste materials can be used as the particles
32/79 precursors for some applications. Waste materials can include, for example, minerals, industrial waste, or an industrial chemical material. Exemplary residual materials include mineral silicate, iron ore, periclase, gypsum, iron (II) hydroxide, fly ash, bottom ash, slag, glass, oil capsules, red mud, battery residue, recycled concrete, refuse, ash paper, or concentrated reverse osmosis brine salts.
[0125] Additional precursor particles may include different types of rock containing minerals such as lime-silicate rock, fitch formation, hebron gneiss, layered gneiss, intermediate member, clayite, quartzite, intermediate Precambrian sediments, feldpatic quartzite, dark in color with smaller limestone beds, high-grade meta-sedimentary biotite shale, biotite gneiss, mica shale, quartzite, hoosac formation, partridge formation, Washington gneiss, Devonian greenvale cove formation, Siluriana, ocoee supergroup, meta-sandstone, meta-grauvaca, Rangeley formation, amphibolites, calcitic and dolomitic marble, manhattan formation, oxidized and gray biotite-quartz-feldspar gneiss, and waterford group.
[0126] Precursor particles can also include igneous rocks such as, andesite, anorthosite, basinite, boninite, carbonatite and charnoquite, sedimentary materials such as, but not limited to, claystone, arcosis, gaps, cataclasite, chalk, clay stone, horny flint , flint, gitsone, lighine, limestone, slime shale, sandstone, shale, and siltsone, metamorphic materials such as, but not limited to, amphibolites, epidiorite, gneiss, granulite, nephrite, corneal, marble, pelite, filite, quartzite, shale, scarnite, slate, talcum carbonate, and soapstone, and other varieties of rocks such as, but not limited to, adamelite, apinite, afanites, borolanite, blue granite, epidosite, phelsites, flint, gemstone, ijolite, jadeitite , jasproide, kenyite, vogesite, larvikite, litchfieldite, luxulianite, mangerite, minette, novaculite, pyrolite, rapakivi granite, porphyry, shonkinite, taconite,
33/79 teschenita, teralita, and variolita.
[0127] Table 1 provides exemplary embodiments of different types of chemicals for the first and second layers that can be obtained when using different precursor materials. With respect to the first layer, using different precursor materials, silica, alumina or titania can be obtained. The second layer can also be modified by selecting the precursor material. For example, the second layer can include various types of carbonates such as, pure carbonates, multi-cation carbonates, carbonates with water or an OH group, carbonates layered with water or an OH group, carbonates containing anion, carbonates containing silicate, and minerals that carry carbonate.
Table 1: Exemplary Precursors and Encapsulating Layers
Raw material (Precursor) First Layer Encapsulating layer Volastonite (CaSiO ₃ ) Rich in silica CaCO ₃ Fosterite (Mg2SiO4) MgCO ₃ Diopside (CaMgSiaOe) (Ca, Mg) CO ₃ Talc (Mg3S40 (OH) 2) MgCOaxHaO (x = 1 - 5) Glaucofanium(Na2Mg3Al2SisO22 (OH) 2) Rich in alumina and / or silica MgCO ₃ and / or NaAICO ₃ (OH) ₂ Paligorsquita ((Mg, AI) 2Si40io (OH) -4 (H ₂ 0)) Mg ₆ Al2CO ₃ (OH) i ₆ 4H2O Meionite (Ca4 (Al2SÍ2O ₈ ) 3 (Cl2CO3, SO4)) Ca2SO4CO ₃ , 4H2O Tanzanite (Ca2AI ₃ O (SiO4) (SÍ2O7) (OH)) CasSiaOsCOs and / or CasSiaOsCOa and / or Ca7SÍ6Oi ₈ CO ₃ , 2H2O (Bao, 6Sro, ₃ Cao, i) Ti0 ₃ Rich in titania Sr (Sr, Ca, Ba) (CO ₃ ) ₂
[0128] The second layer can be modified by introducing additional anions and / or cations. Such additional anions and cations can be used to modify the second layer to increase its physical and chemical properties such as fire resistance or acid resistance. For example, as shown in Table 2, although the first layer is maintained as a layer rich in silica, the second layer can be modified by adding additional anions or cations to the reaction, such as PCU ^2- and SCU ² '. As a result, the second layer can
34/79 include, for example, different phosphate, sulfate, fluoride or combinations thereof.
Table 2: Examples of Cation / Anion Sources (in addition to CO3 ² )
Core Particle First Layer Source ofadditional anion / cation Encapsulating layer Kind ofCarbonate CaSiOa Layer rich in silica Phosphates Ca ₅ (PO4, CO ₃ ) 3OH Phosphate-bearing carbonates Sulfates Ca2SO4CO3,4H2O Sulphate-bearing carbonates Fluorides Ca2CO3F2 Carbonates that carry fluorides Phosphates andfluorides Ca5 (PO4, CO3) 3F Carbonates that carry fluoride and phosphates Source of Mg ^{+2 such} as chlorides, nitrates, hydroxides etc. CaMg (CO3) 2 Multiple cation carbonates A combination of sources ofcation and anion Ca ₆ Mg2 (SO4) 2 (CO ₃ ) 2Cl4 (OH) 4.7H2O Carbonate-bearing minerals post-1992
B2. Bonding matrix and composite material [0129] A bonding matrix comprises a plurality of bonding elements, forming a three-dimensional network. The bonding matrix can be porous or non-porous. The degree of porosity depends on several variables that can be used to control porosity, such as temperature, reactor design, the precursor material and the amount of liquid that is introduced during the transformation process. Depending on the intended application, the porosity can be adjusted to almost any degree of porosity of about 1% by vol. about 99% by vol.
[0130] The bonding matrix can incorporate one or more filler materials, which are mixed with the precursor materials before or during the transformation process to create the composite material. The concentration of elements of
35/79 connection in the connection matrix may vary. For example, the concentration of connecting elements on a volume basis can be relatively high, at least some of the connecting elements are in contact with each other. This situation can arise if the filler material is incorporated into the bonding matrix, but the type of filler material and / or the amount of filler material are such that the level of volumetric dilution of the bonding element is relatively low. In another example, the concentration of linkers on a volume basis may be relatively low, where the linkers are more widely dispersed within the linker such that few, if any, of the linkers are in contact with each other. This situation can arise if the filler material is incorporated into the connection matrix, and the type of filler material and / or the amount of filler material are such that the level of dilution is relatively high.
[0131] In general, the filler material can include any of several types of materials that can be incorporated into the bonding matrix. A filler material can be inert or active. An inert material does not pass through any chemical reaction during transformation and does not act as a nucleation site, although it can physically or mechanically interact with the binding matrix. The inert material can involve polymers, metals, inorganic particles, aggregates, and the like. Specific examples may include, but are not limited to, basalt, granite, recycled PVC, rubber, metal particles, alumina particle, zirconia particles, carbon particles, carpet particles, Kevlar ™ particles and combinations thereof. A chemically active material reacts with the bonding matrix during transformation, passes through any chemical reaction during transformation, and / or acts as a nucleation site. For example, magnesium hydroxide can be used as a filler material and can react chemically with a dissolving calcium component phase
36/79 bond to form magnesium and calcium carbonate.
[0132] The bonding matrix can occupy almost any percentage of a composite material. Thus, for example, the bonding matrix can occupy about 1 vol%. about 99% by vol. of the composite material (for example, the volume fraction of the bonding matrix can be less than or equal to about 90% by volume, 70% by volume, 50% by volume, 40% by volume, 30 % by volume, 20% by volume, 10% by volume). A preferred range for the volume fraction of the binding matrix is about 8 vol%. about 90% by vol. (for example, about 8 vol% to about 80 vol%, about 8 vol% to about 70 vol%, about 8% vol to about 50 vol% ., about 8 vol% to about 40 vol%), and the most preferred range is about 8 vol%. at 30% by vol ..
[0133] A composite material can also be porous or non-porous. The degree of porosity depends on several variables that can be used to control porosity, such as temperature, reactor design, the precursor material, the amount of liquid that is introduced during the transformation process and whether any filler is used. Depending on the intended application, the porosity can be adjusted to almost any degree of porosity of about 1% by vol. about 99% by vol. (for example, less than or equal to about 90% vol., 70% vol., 50% vol., 40% vol., 30% vol., 20% vol., 10% in vol.). A preferred range of porosity for the composite material is about 1 vol%. to about 70 vol%, more preferably between about 1 vol%. and about 10% by vol. for high density and durability and between about 50% by vol. and about 70% by vol. for shallow and low thermal conductivity.
[0134] Within the connection matrix, the connection elements can be positioned, in relation to each other, in any of several orientations. FIGs. 4 (a) to 4 (f) schematically illustrate an exemplary connection matrix that
37/79 includes connection elements in the form of fiber or nameplate in different orientations possibly diluted by the incorporation of filler material, as represented by the spacing between the connection elements. FIG. 4 (a), for example, illustrates a connection matrix that includes fiber-shaped connection elements aligned in a one-direction orientation (“1-D'j (for example, aligned with respect to the x direction). FIG. 4 (b) illustrates a connection matrix that includes nameplate-shaped connecting elements aligned in a two-way ("2-D") orientation (for example, aligned with respect to the x and y directions). 4 (c) illustrates a connection matrix that includes nameplate-shaped connecting elements aligned in a three-direction orientation (“3-D'j (for example, aligned with respect to the x, y and z directions). FIG. 4 (d) illustrates a connection matrix that includes nameplate-shaped connection elements in a random orientation, in which the connection elements are not aligned with respect to any particular direction, Figure 4 (e) illustrates a connection matrix connection that includes a relatively high concentration of platelet-shaped connecting elements that are aligned in an orientation 3-D. FIG. 4 (f) illustrates a connection matrix that includes a relatively low concentration of platelet-shaped connection elements that are situated in a random orientation (a percolation network). The composite material of FIG. 4 (f) obtains the percolation threshold because a large proportion of the connecting elements are touching each other such that a continuous network of contacts is formed from one end of the material to the other end. The percolation threshold is the critical concentration above which connecting elements show long-range connectivity with a regular orientation, for example, FIG. 4 (e), or random orientation, for example, Fig. 4 (f), of connecting elements. Examples of connectivity patterns can be found in, for example, Newnham, et al., “Connectivity and piezoelectricpyroelectric composites”, Mat. Res. Bull. vol. 13, pages 525 - 536, 1978).
[0135] In addition, a hierarchical structure or repetition of levels
38/79 multiple can be obtained in a way that can promote dense packaging, which takes into account the manufacture of a strong material, among other potential functional, useful purposes. The hierarchy describes how structures form patterns at various length scales. Different types of bonding matrices can be created by varying the porosity of the matrix and incorporating core fibers of different sizes. Different types of particulate and fiber components can be used with hierarchical structures to manufacture different types of structures with different connectivity.
C. PROCESSES FOR FORMING BINDING ELEMENTS, BINDING MATRIXES AND COMPOSITE MATERIALS [0136] The transformation (curing) process proceeds by exposing the precursor material to a reactive liquid. A reagent associated with the liquid reacts with the chemical ingredients that make up the precursor particles, and more specifically, the chemical reagents in the peripheral portion of the precursor particles. This reaction eventually results in the formation of the first and second layers.
[0137] In some embodiments, the precursor particles include two or more chemical elements. During the transformation process, the reagent in the liquid preferably reacts with at least one first of the chemical elements, where the reaction between the reagent in the liquid (for example, CO2 and related species in solution) and 0 at least one first chemical element ( eg calcium ²⁺ ) results in the formation of the first and second layers, the first layer comprising a derivative of the precursor particle, generally excluding at least one first chemical element, whereas the second layer comprises a combination (for example, CaCOa ) of the reagent and 0 at least one first chemical element. In comparison, the nucleus comprises the same or approximately the same chemical composition as the particle
39/79 precursor (for example, CaSiOa). For example, peripheral portions of the nucleus may vary from the chemical composition of the precursor particle due to the selective leaching of particular chemical elements from the nucleus.
[0138] Thus, the nucleus and the second layer share at least one first chemical element (for example, calcium ²⁺ ) in the precursor particle, and the nucleus and the first layer share at least one other chemical element in the precursor particle ( e.g. Si ⁴⁺ ). The at least one first chemical element shared by the core and the second layer can be, for example, at least one alkaline earth element (beryllium, magnesium, calcium, strontium, barium and radium). The at least one other chemical element shared by the core and the first layer can be, for example, silicon, titanium, aluminum, phosphorus, vanadium, tungsten, molybdenum, gallium, manganese, zirconium, germanium, copper, niobium, cobalt, lead, iron, indium, arsenic and / or tantalum.
[0139] In some embodiments, the reaction between the reagent in the liquid phase and at least one first chemical element of the precursor particles can be carried out until completion thus resulting in the first layer becoming the core of the linker and having a composition chemistry that is different from that of the precursor particles, and at least one additional or secondary shell layer comprising a composition that may or may not include at least one first chemical element of the two or more chemical elements of the precursor particles.
C1. GAS AIDED HYDROTHERMAL LIQUID PHASE SINTERIZATION [0140] The connection elements can be formed, for example, by a gas-assisted HLPS-based method. In such a method, a porous solid body including a plurality of precursor particles is exposed to a liquid (solvent), which partially saturates the pores of the porous solid body, meaning
40/79 that the pore volume is partially filled with water.
[0141] In certain systems such as those forming carbonate, completely filling the pores with water is believed to be undesirable because the reactive gas is unable to diffuse from the outer surface of the porous solid body to all internal pores by gas diffusion. On the contrary, the reactive gas reagent would dissolve in the liquid and diffuse in the liquid phase from the external surface to the internal pores, which is much slower. This liquid phase diffusion may be suitable for transforming thin porous solid bodies but would be unsuitable for thicker porous solid bodies.
[0142] In some embodiments, a gas containing a reagent is introduced into the partially saturated pores of the porous solid and the reagent is dissolved by the solvent. The dissolved reagent then reacts with at least the first chemical element in the precursor particle to transform the peripheral portion of the precursor particle into the first layer and the second layer. As a result of the reaction, the dissolved reagent is removed from the solvent. However, the gas containing the reagent continues to be introduced into the partially saturated pores to provide additional reagent to the solvent.
[0143] As the reaction between the reagent and the at least first chemical element of the precursor particles progresses, the peripheral portion of the precursor particle is transformed into the first layer and the second layer. The presence of the first layer on the periphery of the nucleus eventually prevents another reaction by separating the reagent and at least the first chemical element from the precursor particle, thereby causing the reaction to effectively stop, leaving a binding element having the nucleus as the center unreacted precursor particle, the first layer on a periphery of the core, and a second layer on the first layer.
[0144] The resulting connecting element includes the core, the first layer and
41/79 the second layer, and is generally larger in size than the precursor particle, filling in the adjacent porous regions of the porous solid body and possibly bonding with adjacent materials in the porous solid body. As a result, the networked formation of products can be formed which are substantially the same size and shape but with a higher density than the porous solid. This is an advantage over traditional sintering processes that cause decreased mass transport to produce a higher density material than the initial compact powder.
C2. HLPS IN AN AUTOCLAVE [0145] In an exemplary embodiment of the HLPS method, a porous solid body comprising a plurality of precursor particles is placed in an autoclave chamber and heated. Water as a solvent is introduced into the pores of the porous solid body by vaporizing the water in the chamber. A cooling plate above the porous solid body condenses the evaporated water which then drips onto the porous body and into the pore of the porous solid body, thereby partially saturating the pores of the porous solid body. However, the method of introducing water in this example is one of several ways that water can be released. For example, water can also be heated and sprayed.
[0146] However, carbon dioxide as a reagent is pumped into the chamber, and carbon dioxide diffuses into the partially saturated pores of the porous body. Once in the pores, the carbon dioxide dissolves in the water, thus allowing the reaction between the precursor particles and the carbon dioxide to transform the peripheral portions of the precursor particles into the first and second layers.
[0147] As the reaction between the second reagent and the first layer progresses, the second reagent continues to react with the first layer, transforming the peripheral portion of the first layer into the second layer. THE
42/79 formation of the second layer can be by exo-solution of a component in the first layer, and such a second layer can be a gradient layer, in which the concentration of one of the chemical elements (cations) composing the second layer varies from high the drop as it moves from the surface of the core particle to the end of the first layer. It is also possible that the second layer could be a gradient composition as well, such as when the layers are amorphous or composed of solid solutions that have constant or varied compositions.
[0148] The presence of the second layer on the periphery of the precursor nucleus eventually prevents another reaction by separating the second reagent and the first layer, causing the reaction to effectively stop, leaving a connecting element having the nucleus, the first layer in one periphery of the nucleus and a second layer in the first layer. The resulting linker is generally larger in size than the original precursor particle, thereby filling in adjacent porous regions of the porous solid body and bonding with adjacent materials of the porous solid body. As a result, the method takes into account the product network formation having substantially the same shape but with a higher density than the original porous solid. This is an advantage over traditional sintering processes that cause decreased mass transport to produce a higher density material than the initial compact powder.
C3. INFILTRATION MEDIA [0149] The infiltration medium used to transport at least a portion of the porous matrix includes a solvent (eg water) and a reactive species (eg CO2). The solvent can be aqueous or non-aqueous. The solvent can include one or more components. For example, in some embodiments, the solvent can be water and ethanol, ethanol and toluene, or mixtures of
43/79 various ionic liquids, such as ionic liquids based on alkyl-substituted imidazolium and pyridinium cations, with halide anions or trialogenoaluminate. Wetting systems are preferred over non-wetting in order to simplify processing equipment.
[0150] The solvent should not be chemically reactive with the porous matrix, although the solvent can react chemically with the reactive species. The solvent can be removed using a variety of separation methods such as mass flow, evaporation, sublimation or dissolution with a washing medium, or any other suitable separation method known to a person of ordinary skill in the art.
[0151] More specifically, the solvent is a liquid at the temperature where the dissolved reactive species reacts with the porous matrix. This temperature will vary depending on the specific solvent and reactive species chosen. Low temperatures are preferred over higher temperatures to save energy and simplify processing equipment thereby reducing manufacturing costs.
[0152] The role of the solvent contrasts with prior art involving reactive systems, such as, for example, Portland cement, where a solvent such as water reacts with a porous matrix to form products containing solvent molecules, such as metal hydrates or hydroxides metals, among other precipitation products.
[0153] Notwithstanding the phase of the pure reactive species, the reactive species dissolves in the solvent as a neutral, anionic or cationic species. For example, at least one reactive species can be CO2, which is a gas at room temperature that can dissolve in water as neutral CO2 but can create reactive species such as H3O ⁺ , HCOa ', H2CO3 and CO3 ² ·. Despite the initial phase of the reactive species and the solvent in its natural state, the infiltration medium is in a liquid phase in the pores (for example, interstitial spaces) of a porous matrix.
44/79 [0154] For example, capillary forces can be used to absorb the infiltration medium in a porous matrix spontaneously. This type of wetting occurs when the infiltration medium has a very low contact angle (for example, <90 ° C). In this case, the medium can partially fill (partially saturate) or completely fill (saturate) the pores. Infiltration can also occur in such a way that some pores are full while others are empty and / or partially full. It is also possible that a porous matrix infiltrated with gradients in filling or pore saturation can later be transformed into one that is uniform through capillary flow. In addition, wetting does not occur spontaneously when the contact angle of the infiltration medium is high (for example,> 90 °). In such cases, fluids will not seep into the porous matrix unless external pressure is applied. This method is useful when it is desirable to remove the infiltration medium by releasing pressure (for example, a reaction can be started or stopped by pressure).
[0155] When the infiltration is done using spontaneous capillary flow in the pores, the mass flow ceases when the pores are full (saturated). During HLPS, the reactive species reacts with the matrix to form one or more products by the various reactions. The at least one kind of reaction is suppressed from within the pore space and thus needs to be replenished during the course of the reaction. When pores are completely saturated with the infiltration medium, the reactive species must be transported from the infiltration medium external to the porous matrix through the matrix pores. In a quiescent fluid, diffusion is the process by which transport occurs. Thus, for some HLPS methods whose reactions within the pores are rapid in relation to all other mass transport processes, the reaction becomes limited by large increases in the thickness of the porous matrix. In such a case, only the outer portion of the matrix reacts extensively with the reactive species, while internal regions of the porous matrix are less
45/79 completely reacted or unreacted. This type of reactions is suitable for the preparation of gradient microstructures where the concentrations of the HLPS process products are higher in the outer portion (near the outer surface regions) versus the interior of the structure.
C4. PROCESS SELECTION AND CONTROL [0156] When highly exothermic reactions proceed slowly in relation to the transport of the infiltration medium and the matrix is thermally insulating, the captured heat can increase the reaction rate inside the matrix to allow its interior to contain more phase product (ie, the product of the reaction between at least one reactive species and a portion of the porous matrix) than its interior. For HLPS processes where reactions areothermally proceed at an intermediate rate in relation to the mass transport of the infiltration medium, the diffusion can continue to provide the pores with reactive species and no gradient in the degree of the reaction (or concentration of the product) will be observed. In such a case, there is little difference in the chemical composition and / or phase from the inside to the outside of the material of the monolithic structure or body.
[0157] In many cases, a uniform microstructure with respect to the phase and composition is desirable in the body of monolithic structure. In addition, it is also desirable to conduct HLPS reactions in a relatively short period of time, for example, where large thick monolithic bodies are needed for applications such as for roads or bridges. It is desirable to balance the reaction rate and mass transport for HLPS processes. The strategy for choosing the precursor and the method of introducing the precursors to understand the infiltration medium is important. The preferred choice of precursors and method of introducing the infiltration medium is at least in part a function of the sample thickness in the thinnest direction, the time scale considered acceptable for the process and the thermodynamic and kinetic restrictions necessary for the process to be
46/79 commercially viable, such as temperature, pressure and composition.
[0158] Table 3 summarizes the choice of precursor and introduction method strategies. The porous matrix can be directly infiltrated or the porous matrix can be evacuated before any of the infiltration sequences described in Table 3. Methods are described that use gases as precursors, liquids as precursors or solids as precursors. In addition, mixtures of phases such as solids and liquids, gases and liquids and gases and solids can all be used. For example, a reagent such as CO2 is a gas in its pure state but is converted to a kind of solution dissolved in water. Such an event can happen by gaseous diffusion in the porous matrix and subsequent condensation when a pore is found. This type of precursor system is relevant when microstructures having carbonate phases are desired. The order of addition of the precursors (solvent and reactive species) can influence the reaction yield and the microstructure of the material.
Fabela 3. Precursors and Methods of Introduction System Reactive species Solvent MaterialDeliquescent Introduction Methods(Reverse / different order can be applied where appropriate) (1) Gas GasPre-mix (parallel introduction) two gases and introduce them at a lower temperature to condense one or more gas species in the matrix to comprise an infiltration solution containing reactive species and solvent or to condense the gas mixture in the matrix by cooling The matrix; orGases can also be introduced in series where one gas is condensed before infiltration or after infiltration and the other is introduced later to dissolve in the liquid phase. (2) Gas Gas Solid Pre-mix the deliquescent solid with matrix, pre-mix the gases (parallel introduction) then flow and / or diffuse the gas mixture through the matrix to form the infiltration solution; orGases can be introduced in series in the pre-mix of deliquescent solid-matrix. The preferred order is to have 0 gas that liquefies
47/79
the deliquescent solid and then the gas that dissolves to form the reactive species. (3) Gas Liquid Solid Pre-mix the deliquescent solid with the matrix, then infiltrate with liquid solvent, followed by adding gas (or visaversa) to form the infiltration solution in matrix pores; orGas and liquid can be pre-mixed as a solution for introducing the deliquescent solid-matrix premix in the pre-mix but the reaction yield can be reduced. (4) Liquid LiquidPre-mix (parallel introduction) fluids then infiltrate the matrix; orInfiltrate fluids through the matrix in series with preferred ordering being liquid solvent before the liquid that supplies the reactive species. (5) Liquid Liquid Solid Pre-mix the deliquescent solid with the matrix, then add the liquid solvent to dissolve the deliquescent solid, followed by adding the liquid reactive species (or visa-versa) to form the infiltration solution; orPre-mix the solvent and the reactive species in liquid phases as an infiltration solution for introduction into the pre-mix of deliquescent solid-matrix (6) Liquid GasInfiltrate the matrix with gas and condense the matrix as a liquid, then infiltrate the secondary liquid into the matrix to mix with the first liquid in the matrix; orThe preferred route is to premix gas and liquid by condensing the gas and mixing it in the secondary liquid, then introducing the solution to a porous matrix (7) Gas LiquidInfiltrate the liquid followed by introducing gas; orPre-dissolve the gas in liquid followed by infiltration (8) Solid SolidMix the solids with the porous matrix, then pressurize or heat to form the infiltration liquid. One solid can flow the other to form a liquid phase that can be removed later by washing. Other solids can be added to reduce the melting temperature to form the liquid phase as long as it can be removed later. (9) Liquid SolidPrepare the infiltration solution by dissolving the solid in liquid,
48/79
followed by infiltration; orPre-mix the solid with the porous matrix, then infiltrate with the liquid (10) Solid LiquidPrepare the infiltration solution by dissolving the solid in liquid, then infiltrating; orPre-mix the solid with the porous matrix, then infiltrate with liquid
[0159] In some embodiments, the solvent and the reactive species can be pre-mixed to form the infiltration medium and then introduced into the matrix in a single step. In other embodiments, it may be preferable to use multiple infiltration sequences. For example, the solvent precursor can be introduced first followed by infiltration of the reactive species or vice versa.
[0160] Neither the solvent precursors nor the reactive species need to be in the same phase initially as the infiltration medium will be a liquid that is found in the pores of the matrix. For example, the solvent precursor can be a vapor such as water, which is gaseous at temperatures of 100 ° C or higher in atmospheric pressure and can be condensed to a liquid by cooling the matrix to a temperature lower than 100 ° C. ° C or using surface energy using porous matrices with pore sizes in the Kelvin pore size range (less than 100 nm). When the pores are large, the temperature is high such that the gaseous species cannot be thermally condensed, small amounts of infiltration solution are required or other reasons not discussed here, and it may be desirable to form the liquid in the pore using a deliquescent compound. Examples of such compounds include boric acid, iron nitrate, and potassium hydroxide. In this case, a vapor such as water can convert the deliquescent solid phase in the pore to a liquid and the crystal growth of the product phase can proceed in the pore. This is particularly useful when the infiltration and diffusion of liquid limits the thickness of the product manufactured by HLPS. Alternatively, gas diffusion can be used to transport the species in
49/79 very large distances to form the infiltration medium necessary for HLPS within the pores of the matrix.
[0161] Various additives can be incorporated to improve the HLPS process and the resulting products. Additives can be solids, liquids or gases in their pure state but soluble in the solvent phase or co-processed (for example, premixed) with the porous matrix before the incorporation of the infiltration medium. Examples include nucleation catalysts, nucleation inhibiting agents, solvent conditioners (eg, water softening agents), wetting agents, non-wetting agents, cement or concrete additives, additives for building materials, morphology control additives crystal, crystal growth catalysts, crystal growth retarding additives, pH buffers, ion concentration adjusters, dispersants, binders, rheological control agents, reaction rate catalysts, electrostatic, steric, electrostatic, polyelectrolytic dispersants and Void layer, capping agents, bonding agents and other surface adsorptive species, acid or basic pH modifiers, additives that generate gas, liquids or solids (for example, when heated, pressurized, depressurized, reacted with another species or exposed to any processing variable not listed here), and biological components or synthetic (for example, serving any of the above functions and / or as a solvent, reactive species or porous matrix).
[0162] In some embodiments, a deliquescent solid can be used. The deliquescent solid can be pre-mixed with the porous matrix. Then the premix of the solvent and at least one reactive species can be introduced to the deliquescent solid-porous matrix. The solvent and at least one reactive species in the premix may be either in the gas phase or both in liquid phases. In some embodiments, the solvent may be a liquid and the at least one reactive species may be in a gas phase in the premix or vice versa.
50/79 [0163] A gas-water vapor stream can be passed over a deliquescent salt in the porous matrix to generate the infiltration medium in a liquid phase in the interstitial space in the porous matrix. For example, a stream of wet gas and water vapor can serve as a solvent for dissolving CO2 and ionizing. A large number of salts are known to be deliquescent and can be used appropriately to form liquid solutions from the flow of moist air over the surfaces of the salt. The selection of the appropriate salt has 0 humidity level in the air. Some salts can operate at very low relative humidity. Examples of deliquescent salts include Mg (NO3) 2, CaCb and NaCI.
[0164] With respect to the release of the infiltration medium, it can be released as a bulk solution that spontaneously moistens the porous matrix. There are many options for releasing this solution. First, the porous matrix can be immersed in the liquid. Depending on the infiltration solution, it can be sprayed onto the porous matrix. In a quiescent system, when there is a volume of infiltration solution that is greater than the pore volume of the porous matrix, the diffusion propagates the reaction releasing the reactive species to the pore sites.
[0165] Alternatively, the fluid can flow (mechanically by convection) through the porous matrix by a variety of methods. Methods such as pressurized flow, drying, electro-osmotic flow, magnetism-osmosis flow, and temperature-driven and chemical gradient flow can be used to flow the liquid infiltration medium through the porous body. This dynamic flow allows the fresh reagent to be close to the porous matrix, as opposed to relying on diffusion processes. This method is beneficial as long as the pore size distribution of the matrix allows for a reasonably high flow rate of a fluid that provides reactive species faster than a diffusional process and is optimal when the delivery rate matches or exceeds the rate reaction for product formation. In addition, the flow through the infiltration medium is
51/79 especially useful for highly exothermic reactions. This is particularly beneficial for monolithic structures that are thick and can generate heat internally capable of generating internal pressures capable of fracturing the monolithic structure.
[0166] There are many applications where material thicknesses exceed this length scale. In these cases, mechanical convection of the fluid by any suitable means known to a person skilled in the art is preferred. An alternative is to introduce the reactive solvent or species as a gaseous species. Also, supercritical conditions can be used to obtain transport rates that are between liquids and gases. Gas species can be mechanically convected by applying a pressure gradient across the porous matrix. If the gas is a reactive species, pores filled with solvent fluid can flow out of the pores leaving behind a film of solvent in the pores that can absorb the gas of the reactive species. Alternatively, partially filled pores will allow gas to flow through the pores as the solvent absorbs a portion of the gas flow through them.
[0167] A system can use low temperatures and low pressures to allow a low cost process. Thus, processes that maintain a fraction of solvent in the pores to facilitate the gas diffusion of the reactive species are preferred over those that use quiescent fluids for reactions where a large fraction of product is desired. There are many device designs that can effectively transport the reagent and solvent species to the pores. Some of these projects involve conventional reactor equipment such as filter presses, spray chambers, autoclaves and steam engines.
D. CO2 HEALING CHAMBERS [0168] The invention provides apparatus and methods for curing low, energy efficient, low-cost carbon footprint of concretes using dioxide
52/79 carbon as a reagent. We now describe the engineering design principles and methods that provide increased carbon capture and utilization with minimal or no cost when compared to traditional Portland cement concrete curing chambers.
D1. CONCRETE CURE USING CO2 [0169] The systems and methods of the invention are used using materials and chemicals that rely on the presence of CO2 to cure, such as CO2 in a reaction medium such as water, in which carbonic acid, carbonate ions , and bicarbonate ions are provided. Examples of such materials and chemicals have been described here above.
[0170] The CO2 concrete curing process described here is generally similar to the conventional concrete curing process described above, with the significant difference that five parameters are independently controlled in the controlled curing environment versus the two originals described in traditional curing. In addition to temperature and humidity, system pressure, carbon dioxide concentration, and gas velocity within the chamber are also controlled. A distinction with respect to moisture control is that in conventional prior art systems, humidity is elevated above the environment because water is a reagent in curing Portland cement, while in systems and methods according to the present invention, water is not a reagent but is preferably a reaction medium. Preferably, in the present systems and methods CO2 is the reagent. Consequently, in the present invention, water vapor, temperature and gas velocity can be controlled to cause water to be removed from the curing product or added to the curing product as may be necessary. Both “large environment” and “multipath” curing systems as described in conventional concrete curing systems can also be used in CO2 curing systems.
53/79 [0171] FIG. 5 is a schematic diagram of a CO2 concrete curing chamber constructed and operated in accordance with the principles of the invention. In FIG. 5 a curing chamber is supplied with CO2 from a source via a metering valve, which can control the pressure, the flow rate, and the duration of the CO2 flow. The CO2 atmosphere is recirculated through a blower and a heat exchanger or heater, so that the temperature of the atmosphere inside the curing chamber can be regulated or modified. In some embodiments, a heat exchanger can be used to cool the atmosphere inside the curing chamber, for example if the curing reaction is sufficiently exothermic so that the atmosphere is being overheated.
[0172] In the described embodiments, industrial grade CO2 in about 99% purity is used, which is supplied by a variety of different industrial gas companies, such as Praxair, Inc., Linde AG, Air Liquide, and others. This supply can be maintained in large pressurized containment tanks in the form of liquid carbon dioxide regulated at the specific temperature such that it even maintains a vapor pressure of approximately 300 PSIG. This gas is then pumped and regulated by pressure in a CO2 curing chamber. Alternatively, CO2 captured in industrial facilities (including but not limited to ammonia production plants, natural gas processing plants, cement manufacturing plants, glass manufacturing plants, landfill CO2 and other biogas, biodiesel plants ) and combustion source installations (for example, production of electricity or steam) can be used. In addition, CO2 produced from carbon dioxide production wells that drill into the earth to extract a stream of carbon dioxide from a geological formation or group of formations that contain carbon dioxide deposits can also be used.
D2. CONCRETE CURE TEMPERATURE CONTROLS
54/79
C0 ₂ [0173] In some embodiments, the temperature is measured using a sensor such as a thermocouple or an RTD. The measurement signal is sent back to a controller or computer that is able to regulate the energy in the heat exchanger and thereby adjust the temperature of the entire system over time. The blower is an important component of the heating system as it is able to help transfer the thermal energy to the gas it transfers to the products and the chamber itself which is an important part of the samples' controlled humidity. The heating method can be electric or gas. Jacket heaters can be used to control the temperature of the CO2 flowing through a chamber in contact with the heating jacket, any convenient source of heat can be used. External heating means may include, but are not limited to, electric heating, hot water heating, or hot oil heating. For CO2 curing chambers, indirect gas heating systems have been used so far and direct-burning gas burners have been avoided because they will draw air and combustion products into the system, thereby diluting 0 CO2 and making control of the CO2 concentration problematic. Some smaller scale systems such as Drum Reactors use electric jacket heaters to heat the entire surface of the chamber rather than a heating element within the chamber.
D3. CO2 CURE OF CONCRETE HUMIDITY CONTROL OPTIONS [0174] FIG. 6 is a schematic diagram of a concrete CO2 curing chamber that provides humidification according to the principles of the invention. In FIG. 6, a water supply is provided and water vapor is added to the atmosphere that is circulating within the curing chamber. Water can be any convenient source of drinking water. In some embodiments,
55/79 ordinary tap water is used. In some embodiments, water can be converted to steam by flow through a spray nozzle or spray nozzle, an electric steam generator, a gas steam generator, or by being heated above the temperature of the gas in the chamber in order to cause evaporation of liquid water provides an example being a drum reactor with an immersion heater. In yet another embodiment, the supply of CO2 can be flowed into the systems after it has been bubbled through a supply of heated water in order to increase the relative humidity of the inlet gas stream an example being a drum reactor configured for “flow” or “open circuit” processing.
[0175] Relative humidity is an important parameter both in traditional concrete curing as well as CO2 concrete curing. In a traditional curing chamber an atmosphere of moist air exists that is comprised mainly of nitrogen, oxygen, and water vapor. In these systems the relative humidity is 0 most often measured by standard capacitive sensor technology. However, CO2 curing chambers have a gas atmosphere comprised predominantly of carbon dioxide that is incompatible with some types of these sensors. Sensing technology such as dry bulb wet bulb techniques that use psychrometric ratios for carbon dioxide and water vapor or dipole polarization water vapor measuring instruments or cold mirror hygrometers or capacitive humidity sensors in CO2 concrete curing systems described here.
[0176] Depending on the type and geometry of the product being cured, the design of the chamber, and the packaging efficiency of the product in the chamber, the humidity may need to be decreased or increased and adjusted to a specific set point. Setpoints can range anywhere from 1% to 99% relative humidity. Three different methods of humidity control may exist
56/79 in CO2 concrete curing processes that can be combined in a single system. The method for humidification in an embodiment of a CO2 curing system is shown in FIG. 6.
[0177] FIG. 7 is a schematic diagram of a CO2 curing chamber that provides dehumidification by purging wet gas according to the principles of the invention. As mentioned, in some cases it is necessary to remove moisture from the system to cure concrete products with CO2. A simple method of reducing relative humidity is to replace the wet gas in the system with a dry gas, in this case carbon dioxide. The mixture of wet CO2 gas is released via an exhaust valve which can be a dosing control valve or an automatic bleed valve, and makes up 0 CCdry which enters the recirculation system in order to decrease the humidity relative to the point desired setting while maintaining regulated pressure and gas flow within the curing system. In this type of purge dehumidification, a disadvantage is that a larger amount of carbon dioxide will be exhausted from the system. However, an advantage is that the amount of water vapor can be conducted down to the water vapor concentration in the inlet purge gas, which in some instances can be extremely low if the CO2 purge gas is generated by vaporization of liquid CO2.
[0178] FIG. 8 is a schematic diagram of a CO2 curing chamber that provides dehumidification using a cooled heat exchanger according to the principles of the invention. In an alternative embodiment, the dehumidifying apparatus and method shown in FIG. 8 represent a technique to reduce the relative humidity and therefore remove the water vapor from the gas by a non-purging method. This particular technique uses a water extraction apparatus and method to remove water, which in a preferred embodiment is a cooled heat exchanger. A recirculating cooling unit circulates a solution
57/79 water and ethylene glycol cooled between -15C and 15C through a high surface area stainless steel heat exchanger coil that is mounted on the direct wet gas flow line. Some of the water in the gas stream will undergo a phase transition and condense to form a liquid in the coil, which can then be collected and drained out of the system via a liquid drain trap, conventional valve, or a valve solenoid on a stopwatch to drain the liquid and not the gas. The benefit of using this type of system is that during the process a very minimal amount of carbon dioxide gas will be ejected and spent when compared to the purging dehumidification method shown in FIG. 7. A disadvantage of this technique is the need for extra equipment that is not standard in traditional concrete curing chambers. Another disadvantage is that the system's energy demand will increase to operate the cooling unit.
[0179] In some situations, for example if there is a need to remove a large amount of water from the system, the two dehumidification methods mentioned above can be operated together to keep humidity levels as low as possible.
D4. FILLING AND RAISING THE CONCENTRATION OF CARBON DIOXIDE IN THE HEALING SYSTEM [0180] At the beginning of a curing process, a period of interruption of previous carbon dioxide with control of parameters such as temperature, relative humidity, and gas velocity can first exist, this point at which concentrations of carbon dioxide can be increased in a curing chamber by flowing CO2 into the gas source system and moving the air out of the chamber, which is called the purging cycle. Throughout the purging cycle, an excess of carbon dioxide will be used which takes into account some still unavoidable waste in the process. In some embodiments, it is expected
58/79 that the outlet gas can be collected and fractionated to recover CO2 that would otherwise be lost through ventilation or transferred to a secondary cure chamber or an additional opening in a multipath cure system. The purge cycle is completed when the desired concentration of CO2 in the curing chamber is reached. CO2 concentration can be measured using a variety of different measurement techniques such as non-dispersive infrared sensing or gas chromatography. Reaction rates in the carbonation cement compositions described here have a strong relationship to the carbon dioxide concentration, and therefore typically high CO2 concentrations are achieved at the beginning of the reaction cycle, but this does not have to be the case at all. examples. After the purge cycle, the relative humidity, temperature, and gas velocity in the chamber can be adjusted to reduce water evaporation from specimens in the chamber if necessary.
[0181] In the embodiments described here, carbon dioxide is a reagent and will be consumed in the process. Therefore, it is important to reinforce the CO2 supply throughout the process in order to maintain a desired reaction rate. After the high flow of CO2 in the chamber in the purge cycle has been completed, some options exist to maintain a high level of CO2 during the reaction.
D5. COUNTING OF CO2 BY CONSTANT FLOW AND BLEEDING (OPEN CIRCUIT) [0182] One technique that can be applied is to use a compatible yet low flow of CO2 for the entire duration of the curing process while bleeding a low flow of exhaust gas. This type of curing system can be the simplest and require the minimum amount of feedback and system control and can be used when a profile is not yet known for a product or when precise control is not necessary. However, it can also be configured in a sophisticated manner that can have flow meters at the entrance
59/79 and exit the system to conduct a CO2 mass balance and determine the total rates and amounts of sequestered CO2 using a computerized control system that can basically indicate the reaction rates and determine when the curing process has been completed. This will allow CO2 concentrations to be replenished. The flow rate of the constitution CO2 needs to be only as high as the rate of gas consumed in the process. The side effect of this method is “purging dehumidification” as described earlier in the beginning using dry gas to entrain wet gas. This process can be implemented by providing a high flow CO2 valve for the purge cycle and a low flow CO2 valve or flow controller for replenishment for the entire duration of the curing cycle, as illustrated in FIG. 9. As described earlier, this methodology for refilling and dehumidifying CO2 requires CO2 in excess of what is required in the reaction.
[0183] This constant flow methodology is called flow through reaction, and is also useful for processes using continuous CO2-rich gas streams. Such residual streams can be flue gases from a variety of industries including but not limited to cement kilns, glass melting furnaces, power plants, biogas, and the like. Therefore, such constant flow chambers can be configured and compatible with both an industrial CO2 gas supply and residual gas streams. Solidia Drum reactors shown in FIG. 12 to FIG. 15 are an example of a small-scale unit that can be used as a low-flow CO2 refueling system.
D6. LOW PRESSURE REGULATED REFUELING [0184] After regulating the CO2 purge, there is another method for maintaining CO2 concentrations for the duration of the curing cycle. This alternative method uses low pressure regulation. In a mechanically
60/79 regulated a low pressure diaphragm regulator is used. This regulator can control pressures up to as low as 1 inch of H2O (or approximately 1/400 of an atmosphere). These regulators are highly sensitive and take into account the CO2 replenishment only as the pressure is reduced due to the consumption of CO2 in the reaction process. An example of this type of system is the Small Scale Solidia Drum Reactor that can be configured for low pressure regulated refueling as well as constant flow refueling.
[0185] In another embodiment, an electronic method can be used by measuring the pressure in the system with a highly accurate low pressure transducer connected with a metering control valve as opposed to a mechanical diaphragm valve. FIG. 10 is a schematic diagram of a curing chamber that has a CO2 purge line and that can provide pressure-regulated CO2 replenishment using this technique. An example of this is the Solidia autoclave system operated at low pressure.
D7. REGULATION OF THE CLOSED CO2 CONCENTRATION CIRCUIT [0186] Another method for prolonging the concentration of carbon dioxide during the reaction is well studied to maintain a highly compatible concentration, although this is the most expensive technique. This method uses the CO2 concentration measurement in the system directly, and employs a controller such as a PLC to control the CO2 concentration at a fixation point with an electronic / automatic control valve. A measurement technique for directly measuring CO2 such as NDIR should preferably be used. In the NDIR measurement method, a gas sample stream is drawn from the system using a low flow pump. A cooler is used to remove moisture from the gas stream before it is experienced by the NDIR instrument.
61/79
Therefore, the measurement provided by the analyzer is losing the water vapor component of the gas stream and needs to be adjusted to account for the moisture that has been removed from the test sample. A measurement of the moisture in the gas flow of the system can be performed using a dry bulb-wet bulb psychrometric technique, as illustrated in FIG. 19 (see the wet bulb humidity measuring device 1930 wet bulb) or using a different type of humidity sensor. The true CO2 concentration can be calculated using the computer control system or PLC. Once the true CO2 concentration is known, the triggered metering control valve can add dry CO2 to the system when it has been consumed and has fallen below the set point that is desired at this point. In various embodiments, the attachment point may vary with time, if necessary, based on experience with specific curing compositions, shape and sizes of concrete specimens.
[0187] FIG. 11 is a schematic diagram of a medium-sized curing chamber with multiple moisture control methods as well as the ability to control and replenish CO2 using constant flow or pressure regulation and which can control moisture according to the principles of the invention.
D8. GAS SPEED CONTROL [0188] Another important control parameter is the gas speed through the material that must be cured in the system which can be very dependent on the number of different aspects including but not limited to the chamber design, deflector design , propeller size, propeller speed / power, number of propellers, temperature gradient within the system, shelf design within the system, and sample geometry within the system. The simplest method for controlling the speed of gas inside the chamber is by adjusting the blower speed (RPM’s), typically done using frequency conduction
62/79 variable to take into account the blower motor speed control. The blower can be used to circulate gas at a desired speed in the curing chamber. The gas velocity in the system is measured in the system using a variety of different techniques including but not limited to measuring Pitot tubes and laser Doppler detection systems. The measurement signal for the gas velocity can be sent back to a computer system or programmable logic controller and used as a control parameter in the cure profile.
APPARATUS EXAMPLES [0189] FIG. 12 to FIG. 20 show various embodiments of apparatus that are constructed and operate according to the description of the inventive systems provided here.
[0190] FIG. 12 is an image of several drum reactors built from 55 gallon stainless acid drums.
[0191] FIG. 13 is an image of the interior of a drum reactor including shelves to support reeds of materials to be processed therein.
[0192] FIG. 14 is an image of the exterior of a drum reactor surrounded by a heating jacket, and showing several thermocouple connectors and a gas inlet port.
[0193] FIG. 15 is an image of a control panel for a drum reactor showing four controllers that control (from left to right) an immersion heater, a jacket heater, an in-line gas heater, and a propeller, with readings for the temperatures of the three heaters.
[0194] FIG. 16 is an image of a commercially available CDS curing chamber (available from CDS Inc, Cinderhill Trading Estate, Weston Coyney Road, Longton, Stoke-on-Trent ST3 5JU, Great Britain) that has been optimized for low CO2 curing. pressure according to the principles of
63/79 invention. In FIG. 16 a 1610 CO2 inlet from a CO2 source such as a tank in the chamber has been added and is illustrated. This is an example of a CO2-regulated curing system called the Solidia Portable Shipping Container Reactor.
[0195] FIG. 17 is an image of a portion of the interior of the chamber of FIG. 16, showing other modifications made to the Portland cement curing system of the prior art. A Dipole 1710 Polarization Moisture Volume Probe was added. A commercially available 1740 non-dispersive infrared (NDIR) CO2 analyzer that allows determination of CO2 concentration has been added (Siemens Ultramat 23, available from Siemens AG, An Internet Plaza, Johnson City, TN 37604). A 1730 sample cooler was added to the flow line that enters this analyzer. The sample cooler draws moisture from the gas stream first so that the sensor can read the CO2 concentration without any interference from water vapor. The 1730 cooler can be used to condense water in the system and to dehumidify the gas stream that is supplied to the system. A 1720 CO2 metering control valve was added, which is used to raise the CO2 concentration and then sustain CO2 levels throughout the course of the curing reaction.
[0196] FIG. 18 is an additional view of the 1740 CO2 NDIR analyzer.
[0197] FIG. 19 is a view inside the curing chamber that illustrates the additional components that have been added. A 1910 dipole polarizing gas sampler that is used to measure the percentage of H2O by volume with extremely high accuracy has been added. A 1920 condensation coil is added to the suction side of the CO2 return duct, before the circulating gas reaches a 50 kW blower and electric heater. The water vapor recovered as a liquid from the cooler inside the return duct is extracted by a condensate drain to dehumidify the flow CO2 gas and
64/79 can be measured using a flow meter to allow measurement of the drying rate of specimens in the chamber. A 1930 dry-wet-bulb moisture measuring device was added, which is similar to an operating hygrometer. The temperature differential between the wet bulb thermometer and the dry bulb thermometer provides a measure of relative humidity. In one embodiment, a programmable logic controller (PLC) is programmed with instructions that provide a relative humidity calculated based on thermal measurements, the psychrometric ratio of the gases, and an equation that represents a vapor in the temperature range being used. The curing chamber is modified by providing a 1940 opening through which the gas is tested at a rate of 1 L / min for analysis on the 1740 CO2 NDIR analyzer (located outside the active portion of the curing chamber). In the example shown in FIG. 19, a 1950 inlet for CO2 gas arriving from a metering valve is provided at the bottom of the curing chamber. In other embodiments, the entry can be located on another face of the chamber, or multiple entries can be used.
[0198] FIG. 20 is a screen capture of the monitor connected to a programmable logic controller or other control device, such as a general purpose programmable computer that operates under the control of a set of instructions recorded in a machine-readable medium. In the embodiment shown, the curing chamber is a pressure vessel that is operated as an atmospheric pressure reactor, using approximately 0.25 PSIG excess pressure from 50 to 99% pure CO2 that is taken as vaporizing a vessel containing high pressure liquid CO2 and most of the remaining water vapor. The automatic control system screen, which can be a touch screen, shows a variety of controls and readings of process variables such as time, temperature, relative humidity, pressure, gas flow rates and so on. The automatic control system provides 0 control of the temperature profile and
65/79 humidity in the presence of high concentration of CO2 gas. When the curing chamber is first charged and started, a CO2 purge system is used to introduce CO2 over the course of 15 minutes, during which time the ambient air in the curing chamber is replaced with CO2. The systems of the invention provide dynamic control in which the temperature, humidity, CO2 concentration, CO2 flow rate, and system pressure are independently controlled throughout the curing cycle, and each can be varied to be increased or decreased independently or dependent on changes in other variables. The controller can record any of the data it displays.
EXAMPLES OF THE HEALING METHOD
Example 1: 6 inch by 9 inch floors cured in a drum reactor in a CO2 atmosphere with self-generated moisture
Raw materials [0199] Synthetic Volastonite (SC-C2), Donghai Golden Resources Industries, Donghai, China; aggregate of ¹ Zi ”false rock from Stavola (NJ), construction sand from Bound Brook (NJ) and Glenium 7500 (BASF). Table 4 provides the mixing ratio of the raw material used to prepare the floors.
Table 4 Mixing proportions (100 kg lot size
Solid components: 94.3%Synthetic Volastonite (SC-C2) 18% 17.1 kg Construction sand 55.2% 52.2 kg ¹ Zi aggregate ” 26.8% 25 kg Liquid components: 5.7%Tap water 98.81% 5.632 kg Glenium 7500 1.19% 0.068 kg
Mixing procedure
1. Measure and load 25 kg of ¹ Zi ”aggregate in a planetary mixer (Sicoma ™ MP375 / 250).
2. Measure and load 55.2 kg of construction sand in the mixer.
3. Measure and load 17.1 kg of Synthetic Volastonite (SC-C2) in the mixer.
66/79
4. Mix the solid components loaded in the mixer for approximately 3 minutes. This generates a dry mixture.
5. Measure and load the liquid component (5.632 kg of water and 0.068 kg of Glenium 7500 as in this example) in the mixer containing the dry mixture, and continue mixing for approximately 2 minutes until the uniform slurry is formed. This generates a moist mixture.
Pressing procedure
1. The wet mixture is discharged into a hopper and transported to the floor forming machine (Columbia Model 1600)
2. The wet mixture is then discharged into the feed tank of the floor forming machine
3. The wet mixture is then discharged from the feed hopper into the floor mold cavity. As the wet mixture is discharged into the floor mold cavity, the mold is vibrated in order to effectively fill the cavity.
4. The compression head of the floor press compresses the wet mixture for approximately 1.5 seconds or until the wet mixture reaches a height of 2 5/8 ”inches. This generates a green ceramic body.
5. The green ceramic body in the form of a floor is then removed from the mold cavity.
Curing procedure [0200] Green ceramic bodies in the form of floors are cured in the drum reactor as follows. The 1.6 kW commercially available heating jacket in contact with the outside of a 55-gallon stainless steel drum is heated to 110 degrees Celsius to preheat the shell for approximately twenty minutes. Green ceramic bodies are loaded onto aluminum sheets and placed on the system shelf set containing a 373 CFM propeller and a deflector system to guide the flow through the samples. The cover that contains a
67/79 V2 ”hole in diameter is sealed around the drum by means of a compression sealing ring. The propeller is started, and a flow ranging from 200 to 500 L / min of CO2 is started, flowing through the system and out of the V2 hole in the cap. After fifteen minutes, the CO2 flow is stopped and the V2 ”port is connected with a low pressure relief setting, exhausting any pressure that exceeds 1/2 PSIG. The heating jacket is controlled to regulate an internal gas temperature of the system to 60C. As the pressure develops from the expansion of gases during heating and the water vapor pressure developed from the evaporation of water in the samples, the low pressure relief setting will intermittently relieve the pressure and exhaust some moist CO2. An alternative CO2 line is open that contains a low pressure regulator that regulates the gas in the drum reactor to 0.33 PSIG. This regulator adds gas to the system if the pressure drops below 0.33 PSIG, which occurs once the thermal equilibrium has been achieved and CO2 is being consumed in the reaction chamber. The relative humidity in the system is sustained in a relatively high amount, in the area of 60 to 96%. After 20 hours, the flow of gas in the system is stopped and the lid is opened. The green ceramic bodies, now converted to cured floors, are removed from the system and contain anywhere from 3 to 5% CO2 by mass, and have compression efforts in the range of 2,000 to 13,000 PSI as tested by ASTM C 936.
Example 2: 6 inch by 9 inch floors cured in a drum reactor in a CO2 atmosphere with condensate drain for dehumidification [0201] Green ceramic bodies in the form of floors are prepared in the same way as in Example 1.
Curing procedure [0202] The curing process described in example 1 is performed while using a solenoid valve on a stopwatch (opens for 5 seconds every 10
68/79 minutes) at the bottom of the drum reactor as to remove condensate at the bottom of the reactor and therefore reduce moisture in the system during the course of the curing cycle. A time is used such that the system is sealed and only the condensate bleeds intermittently without bleeding too much gas out of the system. Liquid drainage siphons can be used but can be challenging to use due to the low gas pressures involved. During this the relative humidity is maintained in the area of 37 to 67%. After 20 hours, the gas flow in the system is stopped and the lid is opened. Cured floors are removed from the system and contain anywhere from 3 to 5% CO2 by mass, and have compression efforts in the range of 2,000 to 13,000 PSI as tested by ASTM C 936.
Example 3: 6 inch by 9 inch floors cured in a drum reactor in a CO2 atmosphere with added moisture by heating the water at the bottom of the chamber [0203] Green ceramic bodies in the form of floors are prepared in the same way as in Example 1.
[0204] The curing process described in example 1 is carried out in which the bottom of the drum reactor is equipped with a 1 kW immersion heater located at the bottom of the drum. The drum is filled with approximately 3 to 5 gallons of water, 0 enough to cover the 1 kW immersion heater. The cap containing a W hole in diameter is sealed around the drum by means of a compression sealing ring. The propeller is started, and a flow ranging from 200 to 500 L / min of CO2 is started, flowing through the system and exiting the W hole in the cap. After ten minutes, the CO2 flow is stopped and the W port is connected with a low pressure relief setting, exhausting any pressure that exceeds 1/2 PSIG. The heating jacket is controlled to regulate an internal gas temperature of the system to 60C. To increase the relative humidity in the system the energy production for the immersion heater is controlled to
69/79 heat the water to 64C which is measured by a separate thermocouple immersed in the water. As the pressure develops from the expansion of gases during heating and the development of water vapor pressure from water evaporation in the samples, the low pressure relief setting will intermittently relieve the pressure and exhaust some wet CO2. An alternative CO2 line is opened that contains a low pressure regulator that regulated the gas in the drum reactor to 0.33 PSIG. This regulator adds gas to the system if the pressure drops below 0.33 PSIG, which occurs once the thermal equilibrium has been achieved and CO2 is being consumed in the reaction chamber. The relative humidity in the system is sustained in a very high amount, in the range of 83 to 99%. After 20 hours, the gas flow in the system is stopped and the lid is opened. Floors are removed from the system and contain anywhere from 3 to 5% CO2 by mass, and have compression efforts in the range of 5,000 to 13,000 PSI as tested by ASTM C 936.
Example 4: 6 inch by 9 inch floors cured in a drum reactor in a CO2 atmosphere with a wet inlet CO2 stream bubbling the gas stream through a hot water system.
[0205] Green ceramic bodies in the form of floors are prepared in the same way as in Example 1.
Curing procedure [0206] Samples are cured in a through-flow drum reactor as follows: The 1.6 kW commercially available heating jacket in contact with the outside of a 55-gallon stainless steel drum is heated to 110 Celsius to preheat the peel for approximately twenty minutes. The samples are loaded onto aluminum sheets and placed on the shelf set system which contains a 373 CFM propeller and a deflector system to conduct the flow through the samples. The cap containing a W hole in diameter is sealed around the drum by means of a sealing ring by
70/79 compression. For this experiment, a diluted CO2 stream is created. A 99.9% industrial food grade CO2 gas stream and compressed air are regulated using a mixing gas rotamer that allows the flow of each gas to be controlled and diluted CO2 concentrations down to the 25 to 40% range with a total flow rate ranging between 20 and 50 L / min. A commercially available 1.1 kw heated steam pressure vessel (pressure cooker) is filled with water and connected to the CO2 inlet. The gas stream is bubbled through the 75C hot water and into the drum reactor, providing a highly moistened gas stream. The water temperature can be controlled to adjust the humidity. The lines leading from the hot steam to the drum reactor are insulated to prevent condensation and can also be traced by heat to an even higher humidity. The propeller is started and a flow is initiated through the system, leaving the W hole in the cap. A constant exhaustion of this wet gas mixture leaves the systems through the W hole in the front cover during the course of the curing cycle. The heating jacket is controlled to regulate an internal gas temperature of the system to 60C and keeps the walls of the systems warm as well as to prevent condensation from the moistened gas stream entering. The relative humidity of the system is sustained in a relatively high amount, in the area of 92 to 98%. After 20 hours, the gas flow in the system is stopped and the lid is opened.
Example 5: Surface block with 18% ground calcium silicate cured in an autoclave at atmospheric pressure in a CO2 atmosphere using a cooler to reduce moisture
Raw Materials [0207] Synthetic Volastonite (SC-C2), Donghai Golden Resources Industries, Donghai, China; Stavola (NJ) ¹ Zi ”false rock aggregate, Bound Brook (NJ) construction sand, Austral Masonry Bottom ash (Australia), dust from the
71/79 crusher from Austral Masonry (Australia), Sika Viscocrete (Sika) and Glenium 7500 (BASF). Table 5 shows the mixing ratio of the raw material used to prepare the floors.
Table 5 Mixing proportions (100 kg lot size)
Solid components 92.61%Synthetic Volastonite (SC-C2) 18% 16.67 kg Construction sand 25.20% 23.33 kg aggregate of ¹ Zi ” 16.10% 14.91 kg Gray background 19.50% 18.06 kg Crusher Dust 21.20% 19.63 kg Liquid components 7.31%Tap water 99.30% 7.26 kg Glenium 7500 0.30% 0.02 kg Sika Viscocrete 0.40% 0.03 kg
Mixing procedure
1. Measure and load 23.33 kg of construction sand in a planetary mixer (Sicoma ™ MP375 / 250).
2. Measure and load 14.91 kg of ¹ Zi ”aggregate into the mixer.
3. Measure and load 18.06 kg of bottom ash in the mixer
4. Measure and load 19.63 kg of dust from the crusher in the mixer
5. Measure and load 16.67 kg of Synthetic Volastonite mixer (SC-C2).
6. Mix the solid components loaded in the mixer for approximately 3 minutes. This generates a dry mixture.
7. Measure and load the liquid component (7.26 kg of water, 0.02 kg of Glenium 7500 and 0.068 kg of Glenium 7500 as in this example) in the mixer containing the dry mixture, and continue mixing for approximately 2 minutes until paste uniform fluid is formed. This generates a moist mixture.
72/79
Pressing procedure
1. The wet mixture is discharged into a hopper and transported to the floor forming machine (Columbia Model 1600)
2. The wet mixture is then discharged from the feed tank of the floor forming machine
3. The wet mixture is then discharged from the feed hopper into the floor mold cavity. As the wet mixture is discharged into the floor mold cavity, the mold is vibrated in order to effectively fill the cavity.
4. The compression head of the floor press compresses the wet mixture for approximately 1.5 seconds or until the wet mixture reaches a height of 2 5/8 ”inches. This generates a green ceramic body.
5. The green ceramic body in the form of a block is then removed from the mold cavity.
Curing procedure [0208] Green ceramic bodies in the form of blocks are formed 3 at a time per panel. Each panel is placed on an aluminum cart and transferred inside a horizontal autoclave with a diameter of 7 ft, length of 12 ft, which has been preheated to 60 ° C by means of a 140PSI indirect steam heat exchanger coil. of vapor pressure. The autoclave was then purged with CO2 gas heated to 75 ° C keeping the top gas vent open while driving a 7.5 horsepower blower at 3600 RPM's while flowing 60PSI of CO2 gas pressure from a containment tank of liquid CO2 in the chamber. Purge is conducted for 12 minutes to achieve a CO2 concentration of 97% by volume. The bleed valve at the top of the autoclave was then closed, and the CO2 pressure inside the autoclave was set to 0 psig and the gas temperature was maintained at 60C. In this embodiment, the relative humidity is not precisely controlled but is manually adjusted. During the first 5
73/79 hours of profile, a high surface area heat exchanger cooled to 4C with an ethylene glycol / water mixture via a 10 kW cooler is exposed to the gas stream that allows the chamber atmosphere to be dehumidified during this duration. Condensed water formed in the chiller is dripped and left the reactor through a commercially available Armstrong liquid drain siphon. After 5 hours the cooler is turned off and the humidity in the system starts to rise and sustain within a range of 60 and 55%. At the end of the 20-hour curing cycle, fresh ambient air is drawn into the curing system by means of a pump and displaces the CO2 in the curing chamber to safely open the chamber door. At the conclusion of the curing cycle some amount of condensed water accumulated at the bottom of the system, considering the majority of the water lost from the blocks.
[0209] Figure 21 is the corresponding temperature and humidity profile for example 5.
Example 6: Block of normal weight cured in the autoclave at atmospheric pressure in a CO2 atmosphere using self-generated humidity
Raw material:
[0210] Synthetic Volastonite (SC-C2), Donghai Golden Resources Industries, Donghai, China; aggregate of ¹ Zi ”false rock from Stavola (NJ), construction sand from Bound Brook (NJ) and Glenium 7500 (BASF). Table 6 shows the mixing ratio of the raw material used for this example.
Table 6 Mixing proportions (100 kg lot size)
Solid components: 93.9%Synthetic Volastonite (SC-C2) 18% 16.902 kg Construction sand 55.2% 51,832 kg aggregate of ¹ Zi ” 26.8% 25,165 kg Liquid components: 6.1%Tap water 98.81% 6.02 kg Glenium 7500 1.19% 0.08kg
Mixing procedure
74/79 [0211] The mixing procedure is similar to the procedure adapted for compressed floors as described in example 1.
Pressing procedure [0212] Similar procedure was used to compress the blocks as mentioned in example 1 for compressed floors with an exception in the geometry of the mold to form the green ceramic body. The dimensions of the compressed blocks were 7 5/8 ”x 7 5/8” x 15 5/8 ”(49% by volume being solid).
Curing procedure [0213] Green ceramic bodies in the form of blocks are formed 3 at a time per panel. Each panel is placed on an aluminum trolley and transferred inside a horizontal 7 ft diameter, 12 ft long autoclave, which has been preheated to 60 ° C by means of an indirect steam heat exchanger coil with 140PSI of steam pressure. The autoclave was then purged with CO2 gas heated to 75 ° C keeping the top gas vent open while driving a 7.5 horsepower blower at 3600 RPM's while flowing 60PSI of CO2 gas pressure from a containment tank of liquid CO2 in the chamber. Purge is conducted for 12 minutes to achieve a CO2 concentration of 97% by volume. The bleed valve at the top of the autoclave was then closed, and the CO2 pressure inside the autoclave was set to 0 psig and the gas temperature was maintained at 60C. During the course of the 8 hour curing cycle, the relative humidity naturally increases up to approximately 70% due to the evaporation of water from the samples and tends to gradually decrease slowly to approximately 65% due to condensation in the system. At the end of the 8-hour curing cycle, fresh ambient air is drawn into the curing system by means of a pump and displaces 0 CO2 from the curing chamber to the safe opening of the chamber door. At the conclusion of the curing cycle some amount of condensed water accumulated at the bottom of the system, considering the majority of the water lost from the blocks.
75/79 [0214] Figure 22 is the corresponding temperature and humidity profile for example 6.
Test [0215] The ceramic body cured in the form of a compressed block was tested for unlimited compressive strength as per ASTM C90. The compressive strength of the prepared blocks was 17.2 MPa (2500 psi).
DEFINITIONS [0216] As used here, the terms "chemical reagent" and "reagent" are all intended to be synonymous, and are used to refer to a chemical species that reacts with another chemical species.
[0217] Recording the results of an operation or data acquisition, such as, for example, recording the results at a particular time or under particular operating conditions, is understood to mean and is defined here as annotating output data in a non volatile to a storage element, machine-readable storage medium, or storage device. Non-volatile machine-readable storage media that can be used in the invention include electronic, magnetic and / or optical storage media, such as magnetic floppy disks and hard drives; a DVD drive, a CD drive that in some embodiments can use DVD discs, either CD-ROM discs (that is, read-only optical storage discs), CD-R discs (that is , single-write, multiple-read optical storage discs, and CD-RW discs (that is, rewritable optical storage discs); and electronic storage media, such as RAM, ROM, EPROM, Compact Flash cards, PCMCIA cards, or alternatively SD or SDIO memory; and the electronic components (for example, floppy drive, DVD drive, CD / CDR / CD-RW drive, or Compact Flash / PCMCIA / SD adapter) that accommodate and read the
76/79 from and / or write to the storage medium. Unless otherwise explicitly reported, any reference here to "record" or "recording" is understood to refer to a non-volatile record or a non-volatile recording.
[0218] As is known to those of skill in machine-readable storage media techniques, new media and formats for data storage are continually being planned, and any convenient, commercially available storage media and corresponding read / write device that can becoming available in the future is likely to be appropriate for use, especially if it provides any of a greater storage capacity, a higher access speed, a smaller size, and a lower cost per bit of stored information. Well-known older machine-readable media are also available for use under certain conditions, such as tape and perforated paper cards, magnetic tape or wire record, optical or magnetic reading of printed characters (eg OCR and magnetically encoded symbols ) and machine-readable symbols such as one- and two-dimensional bar codes. The registration of image data for later use (for example, writing an image to memory or digital memory) can be performed to allow the use of the information recorded as output, as data for display to a user, or as data to be made available for later use. Such elements or digital memory chips can be standalone memory devices, or they can be incorporated within a device of interest. “Writing out data” or “writing an image to memory” is defined here as including transformed data written to registers within a microcomputer.
[0219] “Microcomputer” is defined here as a synonym for microprocessor, microcontroller, and digital signal processor (“DSP”). It is understood that the memory used by the microcomputer, including for example
77/79 instructions for processing data encoded as “firmware” may consist of memory physically within a microcomputer chip or memory external to the microcomputer or a combination of internal and external memory. Similarly, analog signals can be digitized by an autonomous analog to the digital converter (“ADC”) or one or more ADCs or diversified ADC channels can reside within a microcomputer package. It is also understood that field-programmable arrangement chis (“FPGA”) or application-specific integrated circuits (“ASIC”) can perform microcomputer functions, in software emulation, microcomputer hard disk logic, or by a combination of two. Apparatus having any of the inventive aspects described here can operate entirely on a microcomputer or can include more than one microcomputer.
[0220] General purpose programmable computers useful for controlling instrumentation, registration signals and analysis signals or data according to the present description can be any of a personal computer (PC), a microprocessor based computer, a computer portable, or other type of processing device. The general purpose programmable computer typically comprises a central processing unit, a storage or memory unit that can record and read information and programs using machine-readable storage media, a communication terminal such as a wired communication device or a wireless communication device, an output device such as a terminal screen, and an input device such as a keyboard. The terminal screen can be a touch screen, in which case it can function both as a screen device and an input device. Different and / or additional input devices may be present such as a pointing device, such as a mouse or control, and different or additional output devices may be present
78/79 be present such as an announcer, for example a speaker, a secondary screen, or a printer. The computer can drive any one of a variety of operating systems, such as, for example, any of several versions of Windows, or MacOS, or UNIX, or Linux. Computational results obtained in the operation of the general purpose computer can be stored for later use, and / or can be displayed to a user. At a minimum, each microprocessor-based general-purpose computer has records that store the results of each computational step inside the microprocessor, which results are then commonly stored in cache memory for later use, so that the result can be displayed, registered to a non-volatile memory, or used in additional data processing or analysis.
[0221] In this specification and the appended claims, the singular forms "one," "one," and "o", "a" include reference in the plural, unless the context clearly dictates otherwise.
[0222] Unless otherwise defined, all technical and scientific terms used here have the same meaning as commonly understood by a person of ordinary skill in the art. While any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. Methods reported here can be performed in any order that is logically possible, in addition to a particular disclosed order.
INCORPORATION BY REFERENCE [0223] References and citations to other documents, such as patents, patent applications, patent publications, newspapers, books, documents, web content, were made in this disclosure. All such documents are hereby
79/79 incorporated herein by reference in its entirety for all purposes. Any material, or portion thereof, that is said to be incorporated by reference here, but which conflicts with definitions, existing statements, or other disclosure material explicitly presented here is only incorporated as no conflict arises between this incorporated material and the material of the present disclosure. In the event of a conflict, the conflict must be resolved in favor of the present disclosure as the preferred disclosure.
EQUIVALENTS [0224] The representative examples disclosed herein are intended to help illustrate the invention, and are not intended to, and should not be construed to, limit the scope of the invention. In fact, various modifications of the invention and many additional embodiments of it, in addition to those shown and described here, will become evident to those skilled in the art from the full contents of this document, including examples and references to scientific and scientific literature. patent cited here. The examples contain important additional information, exemplification and guidance that can be adapted to the practice of this invention in its various embodiments and equivalents thereof.

权利要求:
Claims (13)
[1]
1. Curing system to cure a material that requires CO2 as a curing reagent, CHARACTERIZED by the fact that it comprises:
a curing chamber configured to contain a material that consumes CO2 as a reagent and that does not cure in the absence of CO2 during curing, said curing chamber having at least one port configured to allow said material to be introduced into said chamber curing chamber and is removed from said curing chamber, and having at least one closure for said door, said closure configured to provide an atmospheric seal when closed so as to prevent contamination of a gas present in said curing chamber by the gas outside said cure chamber;
a carbon dioxide source configured to supply carbon dioxide gas in said curing chamber via a gas inlet port in said curing chamber, said carbon dioxide source having at least one flow regulation device configured to control a flow rate of said carbon dioxide gas within said curing chamber;
a gas flow subsystem configured to circulate said gas through said curing chamber for a period of time when said CO2-consuming material as a reagent is being cured;
a temperature control subsystem configured to control a temperature of said gas within said chamber;
a humidity control subsystem configured to control moisture in said gas within said chamber; and at least one controller in communication with at least one of said carbon dioxide source, said gas flow subsystem, said temperature control subsystem, and said humidity control subsystem, said at least one controller configured to independently control during
[2]
2/4 a period of time when said material that consumes CO2 as a reagent is being cured at least a respective unit of said flow rate of said carbon dioxide gas, of said circulation of said gas through said curing chamber, said temperature of said gas, and said humidity in said gas.
2. Curing system for curing a material that consumes CO2 as a reagent and that does not cure in the absence of CO2 according to claim 1, CHARACTERIZED by the fact that said curing chamber is configured to contain a gas pressure in that which is above atmospheric pressure.
[3]
3. Curing system according to claim 1, CHARACTERIZED by the fact that said at least one flow regulation device comprises at least one of a pressure regulator and a flow controller configured to supply carbon dioxide gas in a rate substantially equal to a selected rate of consumption of said carbon dioxide by said material that consumes CO2 as a reagent during curing, a rate sufficient to purge the ambient atmosphere of said curing chamber in a period of time between 2 and 120 minutes to obtain a target CO2 concentration in a range of 50 to 90% by volume, and a rate substantially equal to a rate of ventilation of said gas from said curing chamber.
[4]
4. Curing system according to claim 1, CHARACTERIZED by the fact that said gas flow subsystem includes a measuring device configured to measure at least one of an amount of carbon dioxide in said gas present in said chamber curing and a gas velocity of said gas present in said curing chamber.
[5]
5. Curing system according to claim 6, CHARACTERIZED by the fact that said measuring device configured to measure a gas velocity is selected from a pilot tube, an orifice plate, an anemometer, and a detection system by laser Doppler.
3/4
[6]
6. Curing system according to claim 1, CHARACTERIZED by the fact that said gas flow subsystem includes a variable speed blower configured to circulate gas at a desired speed in said curing chamber.
[7]
7. Curing system according to claim 1, CHARACTERIZED by the fact that said temperature control subsystem includes at least one of a temperature sensor configured to measure said temperature of said gas in said curing chamber, an exchanger of heat to regulate said temperature of said gas in said curing chamber, a heat exchanger for controlling a temperature of said gaseous carbon dioxide supplied in said curing chamber via said gas inlet port in said curing chamber , and a heater located on an external surface or built in the walls of said curing chamber.
[8]
8. Curing system according to claim 1, CHARACTERIZED by the fact that said humidity control subsystem includes at least one of a measuring device configured to determine a relative humidity of said gas inside said chamber, a condenser configured to reduce said moisture in said gas within said chamber, an exhaust valve configured to reduce said moisture in said gas within said chamber, and a water supply configured to increase said moisture in said gas within said chamber.
[9]
9. Curing system according to claim 1, CHARACTERIZED by the fact that said at least one controller is a programmable logic controller.
[10]
10. Curing system according to claim 1, CHARACTERIZED by the fact that said at least one controller is a general purpose programmable computer that operates under the control of a set of instructions registered in a machine-readable medium.
4/4
[11]
11. Curing system according to claim 1, CHARACTERIZED by the fact that said at least one controller includes a screen configured to display to any user of a duration of a curing cycle, of said flow rate of said carbon dioxide gas, a concentration of carbon dioxide in said curing chamber, a rate of circulation of said gas through said curing chamber, said temperature of said gas, and said moisture in said gas.
[12]
12. Curing system according to claim 1, CHARACTERIZED by the fact that said at least one controller is configured to record any one of the duration of a curing cycle, of said flow rate of said carbon dioxide gas, a concentration of carbon dioxide in said curing chamber, a rate of circulation of said gas through said curing chamber, said temperature of said gas, and said moisture in said gas.
[13]
13. Curing system according to claim 1, CHARACTERIZED by the fact that said at least one controller includes a touch screen.

类似技术:

---

公开号 | 公开日 | 专利标题

---

US10668443B2|2020-06-02|Curing systems for materials that consume carbon dioxide and method of use thereof

---

EP3097405B1|2021-10-20|Method and apparatus for curing co2 composite material objects at near ambient temperature and pressure

---

JP2022031657A|2022-02-22|Composite materials and binding components of calcium silicate by carbonate chloride and their manufacturing methods

---

JP6479805B2|2019-03-06|Foam composite material, its production method and use

---

US10315335B2|2019-06-11|Rapid curing of thin composite material sections

---

US20140272216A1|2014-09-18|Aerated composite materials, methods of production and uses thereof

---

JP2016539064A|2016-12-15|Hollow core articles and composite materials, and methods of making and using them

---

US20140342124A1|2014-11-20|Wood-like composite materials and methods of preparation thereof

---

US20170204010A1|2017-07-20|Novel cement chemistries

---

US10815154B2|2020-10-27|Composite materials, methods of production and uses thereof

---

TW201616260A|2016-05-01|Method and apparatus for the curing of composite material by control over rate limiting steps in water removal

---

BR112020011138A2|2020-11-17|composite materials, their uses and production methods

---

JP7019557B2|2022-02-15|Composite materials and binding components of calcium silicate by carbonate chloride and their manufacturing methods

同族专利:

---

公开号 | 公开日

---

TWI643833B|2018-12-11|

---

US20180093240A1|2018-04-05|

---

AU2014244068A1|2015-10-29|

---

UA119440C2|2019-06-25|

---

NZ713015A|2020-03-27|

---

TW201500329A|2015-01-01|

---

CN105579209A|2016-05-11|

---

CA2904720A1|2014-10-02|

---

EP2969439B1|2021-05-05|

---

WO2014160168A1|2014-10-02|

---

US10668443B2|2020-06-02|

---

MX2015012656A|2016-02-17|

---

JP2016517365A|2016-06-16|

---

EA201591735A1|2016-07-29|

---

US10016739B2|2018-07-10|

---

KR20160007499A|2016-01-20|

---

US20180311632A1|2018-11-01|

---

EP2969439A4|2016-04-27|

---

JP6598818B2|2019-10-30|

---

KR101695746B1|2017-01-12|

---

JP2017196904A|2017-11-02|

---

CN105579209B|2017-09-12|

---

EP2969439A1|2016-01-20|

---

EA032774B1|2019-07-31|

---

US20140322083A1|2014-10-30|

---

ZA201507531B|2017-01-25|

---

IL241628D0|2015-11-30|

---

MX359648B|2018-10-05|

---

IL241628A|2017-09-28|

---

US9221027B2|2015-12-29|

---

CA2904720C|2016-11-29|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

SU88345A1|1949-10-26|1949-11-30|И.В. Курсенко|Steam-carbonization and drying chamber for building products|

---

US4117060A|1973-08-15|1978-09-26|U.S. Terrazzo Panels, Inc.|Method and apparatus for the manufacture of concrete and like products|

---

US4117059A|1974-05-09|1978-09-26|U.S. Terrazzo Panels, Inc.|Method and apparatus for the manufacture of concrete products|

---

SE410101B|1978-01-03|1979-09-24|Malinowski Roman|AT THE MOLDING OF CONCRETE|

---

US4772439A|1981-06-19|1988-09-20|Trevino Gonzalez Francisco|Process of quickly manufacturing critically shaped concrete products of high strength|

---

US4436498A|1982-02-01|1984-03-13|Conger/Murray Systems, Inc.|Apparatus for curing concrete products|

---

US4862827A|1988-06-28|1989-09-05|Wacker-Chemie Gmbh|Apparatus for coating semiconductor components on a dielectric film|

---

JPH02137782A|1988-11-18|1990-05-28|Hikari Kinzoku Eng Kk|Curing method for concrete part or concrete structure and apparatus therefor|

---

US5089198A|1989-02-17|1992-02-18|Cam Sales, Inc.|Method for curing concrete articles|

---

SU1717371A1|1989-06-26|1992-03-07|Проектно-Изыскательский И Конструкторско-Технологический Институт "Киевский Проектстройиндустрия"|Chamber for heat treatment of concrete samples|

---

JPH03161926A|1989-11-21|1991-07-11|Nec Corp|Manufacture of semiconductor device|

---

JPH0593529A|1991-10-01|1993-04-16|Matsushita Electric Ind Co Ltd|Air conditioning system of variable air-flow-rate type|

---

US5660900A|1992-08-11|1997-08-26|E. Khashoggi Industries|Inorganically filled, starch-bound compositions for manufacturing containers and other articles having a thermodynamically controlled cellular matrix|

---

US5549859A|1992-08-11|1996-08-27|E. Khashoggi Industries|Methods for the extrusion of novel, highly plastic and moldable hydraulically settable compositions|

---

US5257464A|1992-12-14|1993-11-02|Trevino Gonzales Francisco|System and method of curing concrete products in a kiln|

---

JP3161926B2|1995-01-09|2001-04-25|株式会社クボタ|Operation structure for work equipment of work vehicle|

---

US5935317A|1995-08-02|1999-08-10|Dpd, Inc.|Accelerated curing of cement-based materials|

---

US5800752A|1996-01-11|1998-09-01|Charlebois Technologies Inc.|Process for manufacture of polymer composite products|

---

EP0873286A1|1996-01-11|1998-10-28|Interlicense Den Haag B.V.|Device and process for the aerobic treatment of organic substances|

---

US5694701A|1996-09-04|1997-12-09|Minnesota Mining And Manufacturing Company|Coated substrate drying system|

---

DE19646991C2|1996-11-14|2000-03-23|Binker Materialschutz Gmbh|Pest control method|

---

US6308436B1|1998-07-01|2001-10-30|The Procter & Gamble Company|Process for removing water from fibrous web using oscillatory flow-reversing air or gas|

---

JP2000264756A|1999-03-12|2000-09-26|Kontekku:Kk|Concrete material curing system|

---

JP3735233B2|2000-04-19|2006-01-18|積水化学工業株式会社|Method for producing inorganic carbonized cured body|

---

JP3212587B1|2000-06-23|2001-09-25|クリオン株式会社|Humidity control building materials|

---

JP4011366B2|2002-02-26|2007-11-21|クリオン株式会社|Molding material manufacturing method and manufacturing apparatus|

---

JP4320182B2|2002-05-07|2009-08-26|積水化学工業株式会社|Carbonated cured body and method for producing the same|

---

ITRM20020504A1|2002-10-04|2004-04-05|Gioia Antonio La|DOUBLE FLOW CAGE DRIER COMPACTOR E|

---

US7225561B2|2002-10-25|2007-06-05|South African Nuclear Energy Corporation Limited|Oxyfluorination|

---

GB0228734D0|2002-12-10|2003-01-15|West Philip J|Fan controller|

---

JP4485774B2|2003-09-26|2010-06-23|田川産業株式会社|Manufacturing method of molded body and manufacturing apparatus using the method|

---

US20050269254A1|2004-05-24|2005-12-08|Roitman Lipa L|[Air and Water Purifying System And Filter Media]|

---

JP2006143531A|2004-11-19|2006-06-08|Ishikawajima Constr Materials Co Ltd|Curing apparatus for hardened body|

---

US7390444B2|2005-02-24|2008-06-24|Wisconsin Electric Power Company|Carbon dioxide sequestration in foamed controlled low strength materials|

---

JP4929747B2|2005-03-28|2012-05-09|コニカミノルタオプト株式会社|Manufacturing method of optical film|

---

DE102006023182A1|2006-05-17|2007-11-22|Siemens Ag|Sensor arrangement for detecting characteristic values of the environment and method for generating corresponding output signals|

---

US7877895B2|2006-06-26|2011-02-01|Tokyo Electron Limited|Substrate processing apparatus|

---

EP2104641B1|2006-12-06|2014-08-06|University of New Brunswick|Hydrogenation of aluminum using a supercritical fluid medium|

---

JP5060791B2|2007-01-26|2012-10-31|独立行政法人森林総合研究所|Method for drying wood, method for penetrating chemicals into wood and drying apparatus|

---

CN101125442A|2007-06-27|2008-02-20|中南大学|Carbon dioxide maintenance method and technology for concrete|

---

EP2190933B1|2007-07-13|2019-09-18|Advanced Ceramics Manufacturing, LLC|Aggregate-based mandrels for composite part production and composite part production methods|

---

CN100465121C|2007-08-17|2009-03-04|济南大学|Carbonization maintenance aerated concrete|

---

EP2217544B1|2007-11-15|2019-12-25|Rutgers, the State University of New Jersey|Method of hydrothermal liquid phase sintering of ceramic materials and products derived therefrom|

---

MY150249A|2007-11-15|2013-12-31|Univ Rutgers|Systems and methods for carbon capture and sequestration and compositions derived therefrom|

---

JP5270145B2|2007-12-19|2013-08-21|鹿島建設株式会社|Method for producing hardened surface layered cement|

---

EP2092831A1|2008-01-25|2009-08-26|Cargofresh AG|System for monitoring and controlling the composition of the atmosphere in a container for transporting food or other sensitive products|

---

US8499471B2|2008-08-20|2013-08-06|The Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno|System and method for energy production from sludge|

---

US9181509B2|2009-05-22|2015-11-10|University Of Wyoming Research Corporation|Efficient low rank coal gasification, combustion, and processing systems and methods|

---

US8407912B2|2010-09-16|2013-04-02|Velico Medical, Inc.|Spray dried human plasma|

---

WO2011053598A1|2009-10-26|2011-05-05|Rutgers, The State University Of New Jersey|Hydroxyapatite with controllable size and morphology|

---

US8747762B2|2009-12-03|2014-06-10|Applied Materials, Inc.|Methods and apparatus for treating exhaust gas in a processing system|

---

US20110182799A1|2010-01-22|2011-07-28|Rutgers, The State University Of New Jersey|Sequestration of a gas emitted by an industrial plant|

---

CA2821776C|2010-12-15|2016-08-23|Carboncure Technologies Inc.|Carbon dioxide sequestration in concrete articles|

---

JP4822373B1|2010-12-17|2011-11-24|中国電力株式会社|Carbonation curing equipment, carbonized concrete manufacturing method and carbon dioxide fixing method|

---

EP2683676A4|2011-03-05|2014-08-13|Univ Rutgers|Bonding element, bonding matrix and composite material having the bonding element, and method of manufacturing thereof|

---

CN103256806B|2012-02-20|2015-09-02|艾默生电气公司|For the apparatus and method of drying material|

---

UA73492U|2012-03-13|2012-09-25|Национальный Технический Университет Украины "Киевский Политехнический Институт"|Steaming chamber|

---

CN102835449B|2012-09-04|2014-01-08|灵武市果业开发有限责任公司|Preservation method for Lingwu long jujube by phase temperature air condition|

---

US8845940B2|2012-10-25|2014-09-30|Carboncure Technologies Inc.|Carbon dioxide treatment of concrete upstream from product mold|

---

KR101272785B1|2012-12-18|2013-06-11|포항공과대학교 산학협력단|A method to eliminate liquid layer using superspeed partcle beam|

---

US20140178513A1|2012-12-23|2014-06-26|Robert Richard Matthews|Non ionic/electrolyte, liquid/gaseous, mechanically refined/nanoparticle dispersion Building Materials/High Wear-Heat Resistant Part Brushes, Windings, Battery Cells, Brake Pads, Die Cast Molding, Refrigeration, Polarized/Integrated Optical, Spectrometric Processors, Central Processor Unit Processors, Electronic Storage Media, Analogous Series/Parallel Circuit Generators/Transceivers, Particulate Matter PM Carbonaceous-Polyamide, Crystalline Silica, and Cellulosic Filament Extraction/Miners Suit|

---

CA2904720C|2013-03-14|2016-11-29|Solidia Technologies, Inc.|Curing systems for materials that consume carbon dioxide|

---

US10351478B2|2014-01-22|2019-07-16|Solidia Technologies, Inc.|Advanced curing equipment and methods of using same|

---

EP3004027B1|2013-06-07|2022-03-09|Solidia Technologies, Inc.|A method of preparing thin composite material sections|

---

CN104681425B|2013-11-29|2018-07-31|细美事有限公司|Substrate board treatment and substrate processing method using same|US9181509B2|2009-05-22|2015-11-10|University Of Wyoming Research Corporation|Efficient low rank coal gasification, combustion, and processing systems and methods|

---

KR101272785B1|2012-12-18|2013-06-11|포항공과대학교 산학협력단|A method to eliminate liquid layer using superspeed partcle beam|

---

EA031720B1|2013-03-13|2019-02-28|Солидия Текнолоджиз, Инк.|Pavers and construction block composite materials and methods of preparation thereof|

---

EA201591671A1|2013-03-13|2016-07-29|Солидия Текнолоджиз, Инк.|AERED COMPOSITION MATERIALS, METHODS OF THEIR RECEIVING AND APPLICATION|

---

US9393715B2|2013-03-13|2016-07-19|Solidia Technologies, Inc.|Composite railroad ties and methods of production and uses thereof|

---

US10781140B2|2013-03-14|2020-09-22|Solidia Technologies, Inc.|Method and apparatus for the curing of composite material by control over rate limiting steps in water removal|

---

CA2904720C|2013-03-14|2016-11-29|Solidia Technologies, Inc.|Curing systems for materials that consume carbon dioxide|

---

US10351478B2|2014-01-22|2019-07-16|Solidia Technologies, Inc.|Advanced curing equipment and methods of using same|

---

US9938189B2|2013-06-07|2018-04-10|Solidia Technologies, Inc.|Pervious composite materials, methods of production and uses thereof|

---

CA2921642C|2013-08-21|2021-08-03|Solidia Technologies, Inc.|Aerated composite materials, methods of production and uses thereof|

---

EP3052454B1|2013-10-04|2020-03-11|Solidia Technologies, Inc.|Hollow core slabs and method of production thereof|

---

KR102091678B1|2013-11-06|2020-04-24|럿거스, 더 스테이트 유니버시티 오브 뉴저지|Production of monolithic bodies from a porous matrix using low temperature solidification in an additive manufacturing process|

---

CN104681425B|2013-11-29|2018-07-31|细美事有限公司|Substrate board treatment and substrate processing method using same|

---

WO2015090533A1|2013-12-18|2015-06-25|Heidelbergcement Ag|Method for producing binders containing wollastonite|

---

EP3177578B1|2014-08-04|2020-04-08|Solidia Technologies, Inc.|Carbonatable calcium silicate compositions|

---

BR112017002432A2|2014-08-05|2017-11-28|Solidia Technologies Inc|Method and apparatus for curing composite material by controlling rate limitation steps in water removal|

---

WO2016054602A1|2014-10-03|2016-04-07|Solidia Technologies, Inc.|Composition carbonatable calcium silicate cement containing hydrating materials|

---

RS60652B1|2015-02-23|2020-09-30|Palic Marko|Vacuum rotary automatic dryer for fruit, vegetables, cereals, herbs, medicaments and granulates|

---

CN108137410A|2015-03-20|2018-06-08|索里迪亚科技公司|Composite material and binding member and its method from calcium silicates carbonating|

---

US10695949B2|2015-05-18|2020-06-30|Solidia Technologies, Ltd.|Lightweight composite materials produced from carbonatable calcium silicate and methods thereof|

---

EP3463776A4|2016-05-31|2020-01-22|Solidia Technologies, Inc.|Conditioned curing systems and processes thereof|

---

BR112019005963A2|2016-09-26|2019-06-18|Solidia Technologies Inc|improved healing equipment and its methods of use|

---

CN106824710A|2016-12-28|2017-06-13|广东长盈精密技术有限公司|Conducting resinl solidification equipment|

---

CN110662723A|2017-03-23|2020-01-07|索里迪亚科技公司|Carbonatable calcium silicate-based cement and concrete containing mineral additive and production method thereof|

---

US10422579B2|2017-05-02|2019-09-24|Auto Cure Llc|Automated drying and curing chamber|

---

EP3713896A1|2017-11-21|2020-09-30|Solidia Technologies, Inc.|Compositions and method to improve the durability of calcium silicate-based cements and concretes|

---

US20190152858A1|2017-11-21|2019-05-23|Holcim Technology Ltd|Compositions and method to improve the aesthetics of calcium silicate-based cements and concretes|

---

EP3713895A1|2017-11-21|2020-09-30|Solidia Technologies, Inc.|Compositions and method to improve the strength development of calcium silicate-based cements and concretes|

---

CA3083371A1|2017-12-04|2019-06-13|Solidia Technologies, Inc.|Composite materials, methods of production and uses thereof|

---

US10894743B2|2017-12-27|2021-01-19|Saudi Arabian Oil Company|Method for enhancement of mechanical strength and CO2 storage in cementitious products|

---

CN108340480B|2018-01-24|2019-07-09|浙江大学|A method of utilizing carbon dioxide step mineralising curing concrete building block|

---

CN109265037B|2018-11-09|2019-11-22|山东大学|A kind of apparatus and method gathered materials based on in-situ preparation C-S-H intensifying regenerating|

---

CN109542038A|2018-12-27|2019-03-29|魏贵英|A kind of control system and automatic manufacturing method based on reaction kettle production epoxy resin|

---

EP3722058A1|2019-04-07|2020-10-14|Herrenknecht Aktiengesellschaft|Production system and method for producing a concrete segment of a tunnel excavation system|

---

US11254028B2|2019-05-20|2022-02-22|Saudi Arabian Oil Company|Systems and processes for accelerated carbonation curing of pre-cast cementitious structures|

---

WO2021022171A1|2019-08-01|2021-02-04|The Regents Of The University Of Michigan|Methods of making sustainable ductile cast cementitious structure for carbon dioxide sequestration|

---

CN112809897A|2019-09-15|2021-05-18|陈程|Concrete precast pile steam curing system and curing method|

---

TWI723642B|2019-11-22|2021-04-01|哈伯精密股份有限公司|Cooling device|

---

US11236517B2|2019-12-23|2022-02-01|Saudi Arabian Oil Company|Cementitious print head, 3D printing architecture, and cementitious printing methodology|

法律状态:
2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2020-10-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-10-19| B350| Update of information on the portal [chapter 15.35 patent gazette]|

---

2021-12-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2022-03-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201361785226P| true| 2013-03-14|2013-03-14|

---

PCT/US2014/025958|WO2014160168A1|2013-03-14|2014-03-13|Curing systems for materials that consume carbon dioxide|

---