巴西专利BR112016001196B1 method and system for preparing a gas rich in hydrogen from solid organic materials

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专利摘要:
"METHOD AND SYSTEM FOR THE PREPARATION OF A GAS RICH IN HYDROGEN FROM SOLID ORGANIC MATERIALS" The present invention provides a method for the preparation of a gas rich in hydrogen using solid organic materials which includes: solid organic raw materials are heated in a pyrolysis reaction device to perform a pyrolysis reaction; and the gaseous product generated from the pyrolysis reaction performs gasification with steam in a mobile bed gasification device to generate a product rich in hydrogen. The present invention further provides a system for preparing a gas rich in hydrogen using solid organic materials which includes: a dedusting device for classification of a solid heat carrier; a pyrolysis reaction device; a mobile bed gasification reaction device; a combustion reactor and riser. The method of the present invention is operated at atmospheric pressure and the technology is simple, which is suitable for the gasification and co-gasification of various highly volatile solid organic materials, including raw materials that contain a relatively large amount of moisture, mineral substance and sulphur content.
公开号:BR112016001196B1
申请号:R112016001196-1
申请日:2014-07-25
公开日:2020-11-10
发明作者:Shaoping Xu；Yahui Xiao；Chao Wang；Guangyong Wang；Tursun Yalkunjan；Kam Shing Siu；Bin Xu；Connie Hiu Ying Chow
申请人:Dalian University Of Technology；Eco Environmental Energy Research Institute Limited；
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TECHNICAL FIELD
[0001] The present invention relates to the field of the chemical and energy industry. It refers to a method for preparing a gas rich in hydrogen through gasification with vapor of solid organic raw materials and mixing them, using a circulated solid heat carrier as a heating medium, catalyst and filter material to filter and remove dust simultaneously. TECHNICAL FUNDAMENTALS
[0002] It is an ideal model to prepare a gas rich in hydrogen through gasification with vapor of solid organic matter. In order to accomplish this, at least two problems need to be solved: supplying the heat required by steam gasification and eliminating or reducing the tar in the product gas.
[0003] Patent for Invention No. CH ZL200610113063.3 discloses a separating fluidized bed gasification device and method: the fluidized bed reactor is divided into two interconnected environments, in which one environment is used primarily for drying and pyrolysis of solid fuel and the other is used for semi-gasification of gas and modification of tar and hydrocarbon. The heat required by pyrolysis and gasification is provided through the combustion reaction of raw materials and semi-coke with air or oxygen, which are fed in the same reaction space. The patent also provides a double fluidized bed reaction method and device distinguished by the use of solid heat carrier circulation, in which the heat required by pyrolysis and gasification is partially supplied by combustion of unreacted semi-coke in another bed reactor. fluidized. Due to the use of internal combustion for the heat supply, the gas of the gasification product would definitely comprise inert nitrogen, except when a pure oxygen gasification agent is used. The limitation of the fluidized gasification reactor is also found in: low reaction temperature; short residence time, which causes insufficient conversion of tar and hydrocarbon; and high dust concentration of the product gas. In addition, part of the raw materials is burned directly to supply heat, and thus hydrogen is converted mainly to water, instead of efficiently entering the hydrogen-rich product gas, which is unacceptable from the point of view of element usage.
[0004] The Vienna University of Technology, Austria, developed a biomass gasification process with a Fast Internally Circulating Fluidized Bed (FICFB) (reference: http://www.ficfb.at/) The structure of the gasification reactor in FICFB consisted mainly of two reaction spaces: a pyrolysis / gasification zone in a bubbling fluidized bed and an elevation / combustion zone in a fluidized bed, and the solid heat transporter was circulated within those spaces. The solid heat carrier is heated through the combustion of a semi-coke in the combustion zone and is circulated back to the pyrolysis and gasification zone to supply the heat required by steam gasification and biomass pyrolysis in the pyrolysis zone and in the gasification zone. Then the solid heat carrier is fed back to the combustion zone to start the next cycle. The gases in the two zones are separated from one or therefore, a gas rich in hydrogen without nitrogen because it is produced. Pyrolysis and gasification with FICFB technology are carried out in the same reaction space, in which it is difficult to achieve independent control over pyrolysis and gasification, and there are limitations regarding the adaptability of different raw materials. Both the residence time of the biomass pyrolysis volatile matter in the fluidized bed gasification reactor and the contact time of the volatile matter with the solid heat carrier are short, which led to insufficient tar conversion and high tar content. product gas, so the improvement of gasification efficiency is limited. When biomass, young lignite, etc. are used as raw materials, the gaseous product generated would have a large amount of dust due to the spraying of the raw materials during the pyrolysis gasification process. If the dust cannot be removed efficiently in a hot condition, the dust and tar in the gaseous product will form a viscous mixture in the next condensation / purification process, which affects the normal functioning of the system.
[0005] The Patent for the Invention nr CH ZL200710011214.9 provides a method that allows an independent control of the pyrolysis of solid fuel raw materials, the further decomposition and conversion of tar and hydrocarbon in the gaseous product generated through pyrolysis and the supply of heat to reactions by burning the semicoke from pyrolysis. The method is achieved by circulating a solid heat transporter inside tandem reactors, which are the mobile bed pyrolysis reactor, the mobile bed gasification reactor and the combustion reactor and riser pipe. The reactions respectively carried out inside the three reactors are: the pyrolysis of raw materials of solid fuel, the gasification with vapor of gaseous product (including tar and low carbon hydrocarbon) generated through pyrolysis and the combustion of semi-coke and reheating and elevation of the solid heat carrier. The limitation of the method is: since the pyrolysis reactor and the gasification reactor are connected in tandem, consequently the solid heat carrier of the combustion reactor and riser pipe passes through the pyrolysis reactor and the gasification reactor, and then returns combustion reactor and riser; therefore, the operating conditions of the pyrolysis reactor and the gasification reactor are restricted to each other. The temperature of the solid heat carrier fed to the pyrolysis reactor depends entirely on the degree of reaction within the gasification reactor, and the types and amount of solid heat carrier fed to the pyrolysis reactor and the gasification reactor cannot be controlled in any way. independently, respectively. Therefore, it is difficult to achieve a situation in which both the pyrolysis reactor and the gasification reactor operate under the respective optimal operating conditions. SUMMARY
[0006] To solve the above questions, the present invention provides a method and a device for the preparation of a gas rich in hydrogen through gasification with vapor of solid organic matter. Using the circulation of a solid heat carrier, an independent and optimized control of rapid pyrolysis of solid organic raw materials and catalytic conversion and decomposition involved with tar and hydrocarbon vapor within the gaseous product generated by the pyrolysis can be achieved.
[0007] The technical solutions of the present invention are presented below:
[0008] A method for preparing a gas rich in hydrogen through steam gasification of solid organic raw materials is revealed, with which a rapid pyrolysis of solid organic raw materials and the catalyzing of gasification with vapor of the gaseous product generated by pyrolysis can be achieved respectively using the circulation of solid heat carrier. The pyrolysis reaction device and the mobile bed gasification device of the present method are arranged in parallel. The pyrolysis reaction device has a pyrolysis reactor or at least two parallel pyrolysis reactors, and the mobile bed gasification device has a mobile bed gasification reactor or at least two parallel mobile bed gasification reactors, wherein each pyrolysis reactor corresponds to at least one mobile bed gasification reactor, or each mobile bed gasification reactor corresponds to at least one pyrolysis reactor; wherein the gaseous product of each of the pyrolysis reactors is fed to the corresponding mobile bed gasification reactor. The pyrolysis reactor can be a moving bed pyrolysis reactor or a fluidized bed pyrolysis reactor, preferably a moving bed pyrolysis reactor.
[0009] A part of the solid heat carrier is used as a heating medium to heat the solid organic raw materials to be reacted. The other part is used as a heating medium for gasification and, at the same time, it can also be used as a catalyst for gasification and particle filter material to capture the dust entrained in the gaseous pyrolysis product. Preferably, the portion of the solid heat carrier with smaller average particle size is used as a heating medium to heat solid organic raw materials to allow rapid pyrolysis of the raw materials in order to obtain a solid product and a gaseous product. The other part of the solid heat carrier with a larger average particle size is used as a heating medium and to capture dust entrained in the gaseous product generated from pyrolysis and, at the same time, it is used as a catalyst to allow gasification between the gaseous product generated from pyrolysis and steam in order to decompose and convert low carbon tar and hydrocarbon into hydrogen-rich gas. The two parts of the solid heat transporter with low temperature, whose temperatures have been reduced due to the participation of the pyrolysis and gasification process, are joined to be heated and raised. The high temperature solid heat carrier that has been heated is subjected to dust removal and particle classification and is divided into two parts; then, the two parts of the high temperature solid heat carrier that have, respectively, smaller and larger average particle size are respectively used again for pyrolysis and gasification to form a cycle.
[0010] Specifically, the pyrolysis operation includes: pyrolysis of solid organic raw materials is carried out in the pyrolysis reaction device. The solid organic raw materials are quickly mixed with the high temperature solid heat carrier with smaller average particle size in the mixing section of the pyrolysis reaction device and are quickly transferred to the reaction section of the pyrolysis reaction device. During this process, the solid organic raw materials are heated quickly to the pyrolysis temperature, that is, 400 ° C to 800 ° C. The decomposition reaction of solid organic raw materials that have been heated to the pyrolysis temperature occurs in the reaction section of the pyrolysis reaction device to generate a gaseous pyrolysis product (including tar vapor and low carbon hydrocarbon) and a solid pyrolysis product, wherein the solid pyrolysis product has carbon residue. In addition, some components of the gaseous pyrolysis product further react, which is called a secondary reaction, to generate a carbon deposit attached to the solid heat carrier particle. The mixture of the solid pyrolysis product and the solid low temperature heat carrier exits the device for pyrolysis reaction through a quantitative delivery valve under the effect of gravity, and it is fed to the combustion reactor and riser. The gaseous product generated from pyrolysis together with the steam fed to the pyrolysis device is extracted from the pyrolysis reaction device and fed to the mobile bed gasification device.
[0011] The function of the pyrolysis operation is: on the one hand, the volatile organic matter in the solid organic raw materials can be entirely converted into a gaseous product which is then converted into a hydrogen-rich gas by vaporizing the product gaseous during the gasification operation; on the other hand, the pyrolysis of solid organic raw materials generates a moderate amount of carbon deposit and solid product with carbon residue.
[0012] In the previous method, solid organic raw materials are selected from biomass, polymeric solid waste, coal, petroleum coke or combinations of two or more of these. Biomass means fodder and woody plants consisting of cellulose, hemicellulose and lignin, for example, agricultural manure (eg straw, bagasse and rice husk), forestry manure (eg tree bark, core bark and wood chips) or energy culture (for example, miscanthus and pennisetum hydridum), etc. Preferably, solid organic materials used as a single raw material or used for mixed raw materials should have a relatively high amount of volatile material, which is preferably between 20 and 70% (present in a mass fraction with ash-free base) dried). The upper moisture limit of the raw materials must be appropriate to ensure that the raw materials are transported smoothly to the mixing section of the pyrolysis reaction device. The moisture of the raw materials enters the device for gasification reaction in a mobile bed together with the gaseous product generated from pyrolysis, and participates in the catalysis of the gasification with steam of the gaseous product generated by pyrolysis. Therefore, a moderate amount of moisture contained in the raw materials can reduce the additional amount of water.
[0013] In the pyrolysis operation, an appropriate heating rate of the raw material and the pyrolysis temperature are also required. These mainly depend on the composition and particle size of the raw materials, the particle size and temperature of the solid heat carrier and the ratio and mixing rate between the solid heat carrier and the raw materials. Under the condition that the composition of the solid organic raw materials and the particle size and temperature of the solid heat carrier are determined, the temperature of the pyrolysis reaction device can be adjusted by controlling the mixing ratio between the heat carrier. solid heat and raw materials, so that the degree of pyrolysis of solid organic raw materials can be controlled. While the pyrolysis reaction device works in a moving bed mode, in a unit of time the mass ratio between the solid heat carrier fed to the pyrolysis reaction device and the solid organic raw material should be 2 to 7: 1. According to the specific experiment and analysis of the inventor of the present Order, depending on the practical situation the specific ratio can be chosen specifically as 2: 1, 3: 1, 4: 1, 5: 1, 6: 1 or 7: 1, preferably 3 to 5: 1. The temperature of the pyrolysis reaction device must be controlled within the range of 400 to 800 ° C, preferably from 500 to 700 ° C. The higher the temperature of the solid heat carrier, the greater the mass ratio that can be achieved between the solid heat carrier and the solid organic raw material when fed to the pyrolysis reaction device. While the pyrolysis reaction device operates in fluidized bed mode, in order to ensure that the solid organic raw materials can achieve a required degree of pyrolysis the mass ratio between the solid heat carrier and the solid organic raw materials must be increased, and the ratio can be as high as 40 or more. The smaller particle size of solid organic raw materials is advantageous for rapid heating and decomposition. The appropriate upper particle size limit of the solid organic raw materials of the method of the invention depends on whether the solid pyrolysis product can be lifted without difficulty in the combustion reactor and riser, and should typically be controlled below 8 mm. According to the specific experiment and analysis of the inventor of the present Order, based on the practical situation, the particle size can be specifically chosen as 2 mm, 6 mm or 7.5 mm, and preferably the particle size must be controlled below 3 mm.
[0014] Steam, which is one of the raw materials for gasification, is fed from the lower portion of the solid material layer in the pyrolysis reaction device. The benefits are: a gaseous pyrolysis product loaded with vapor of solid organic raw materials quickly leaves the pyrolysis reactor, which promotes the pyrolysis reaction and reduces the secondary reaction of the gaseous product produced by pyrolysis in order to reduce the possibility of generation of carbon and carbon black deposits. While the pyrolysis reactor works in fluidized bed mode, steam is used at the same time as a fluidizing medium and a gaseous heat carrier. In order to ensure that the pyrolysis reactor can reach the required temperature, the temperature of the superheated steam fed to the pyrolysis reactor must be high enough, which is typically controlled above 300 ° C; at the same time, the mixing ratio between the solid heat carrier and the solid organic raw materials fed to the pyrolysis reactor must be increased appropriately, and a small amount of oxygen can also be fed to the pyrolysis reactor at the time of steam supply if necessary.
[0015] The gasification operation includes: in a device for mobile bed gasification reaction, through the use of heat and the reaction surface provided by the high temperature solid heat carrier, the tar and the low carbon hydrocarbon in the gaseous product generated from pyrolysis in the pyrolysis reaction device, it undergoes an additional cracking reaction and reacts with the steam to generate a gaseous product rich in hydrogen; at the same time, a carbon deposit is usually formed on the surface of the solid heat carrier. The hydrogen rich gas product is collected by separating the unreacted water and the residual tar from the gaseous product through the condensation cooling device. As long as the solid heat carrier that has a catalyst activity is employed, through the catalysis of the solid heat carrier, the cracking of tar and low carbon hydrocarbon in the gaseous pyrolysis product and the reaction with steam can be improved in a relatively low temperature. While the gaseous product generated from pyrolysis flows through the mobile bed gasification device, the dust entrained in the gaseous product is captured by the particle bed layer of the solid heat carrier. The solid temperature conveyor with reduced temperature leaves the gasification reaction device and is sent to the combustion reactor and riser together with the captured dust.
[0016] The main function of the gasification operation is to react the tar and low-carbon hydrocarbon of the gaseous product generated from pyrolysis with steam, which must decompose and convert them into a gas rich in hydrogen. The reaction is a highly endothermic reaction, so the basic conditions to ensure that the reaction happens smoothly are high temperature, the catalyst and the efficient distribution and permanence of the reagent in the catalyst bed layer. The temperature of the mobile bed gasification device is normally controlled at 800 to 950 ° C. In a specific condition, for example, although the target product is a gaseous product with a high concentration of hydrogen and calcium oxide being used as a carbon dioxide adsorbent, the lower temperature limit of the mobile bed gasification reaction can be as low as 700 ° C. In circumstances where the operating condition of the pyrolysis reaction device is determined, the temperature of the mobile bed gasification reaction device can be adjusted by means of the temperature and circulation rate of the solid heat carrier fed to the reaction device. gasification.
[0017] The amount of solid heat carrier fed to the mobile bed gasification device can be determined according to the influence of dust removal efficiency and the carbon deposition status of the solid heat carrier on the efficiency of the catalyst of the solid heat carrier that is used as a catalyst. In order to ensure the energy balance of the reaction system, increasing the circulation rate of the solid heat carrier in the gasification reaction device is advantageous to shorten the residence time by reducing the carbon deposit on the heat carrier. solid that is a catalyst in order to avoid permanent catalyst inactivation due to excessive carbon deposit. Controlling the proper circulation rate of the solid heat carrier can prevent excessive resistance of the bed layer due to the capture of dust, while ensuring efficient dust removal from the moving particle layer. In unit time, the mass ratio between the solid heat transporter fed to the mobile bed gasification device and those fed to the pyrolysis reaction device must be controlled at 0.1 to 5. According to the experiment and analysis specific to the inventor of the present Order, based on the practical situation, the ratio can be specifically chosen as 0.5, 1, 3 and 4.5, with which the present invention can be realized.
[0018] In the mobile bed gasification reactor, the mixture between the gaseous product generated from pyrolysis in the pyrolysis reaction device and the vapor comes into contact with the moving particle layer of the solid heat carrier in a contact mode selected from a group consisting of parallel current, counter current, radically crossed current or combinations of the above gas / solid contact and flow mode. When the iron-based or nickel-based catalyst is used with the solid heat carrier, the gas / solid contact mode of countercurrent or cross current is radically advantageous for the self-reduction of the catalyst (ie in a reduced atmosphere , the metal oxide in the conveyor is reduced to a pure metal that has catalyst activity) and to improve the residence time for an efficient reaction. In addition, the radically crossed current moving solid heat carrier particle bed layer also has many advantages: large contact area of the gas / solid phase in the unit volume of the reactor, low flow rate of gas passing through the bed layer moving particle, decreased resistance and so on. Therefore, the radically crossed current moving solid heat carrier particle bed layer is preferred for the method of the present invention. The use of a mobile gasification reactor in a radically crossed current can also efficiently capture the dust entrained in the gaseous product of pyrolysis.
[0019] The heating and lifting operations include: at the bottom of the combustion reactor and riser, the mixture between the solid product generated from pyrolysis in the pyrolysis reaction device and the solid heat carrier with carbon deposit, together with the solid heat carrier with carbon deposit from the mobile bed gasification device, it is fluidized and lifted by hot air. During the lifting process, the carbon residue from the solid product and the carbon deposit on the surface of the solid heat carrier are burned to generate heat and flue gas. The solid heat carrier is heated by the heat generated to provide a high temperature solid heat carrier. The high temperature solid heat carrier and the generated dust-laden hot combustion gas enter the dedusting device for classification of solid heat carrier.
[0020] The main function of the combustion reactor and riser is to regenerate the solid heat carrier, which is as a heating medium, catalyst and moving particle filter material, while the solid heat carrier is lifted by the air flow. hot. The mixture between a solid low temperature heat carrier and the solid product generated from pyrolysis that exits the device for pyrolysis reaction is fed to the bottom of the combustion reactor and riser; at the same time, the low temperature solid heat transporter, which already captures dust and leaves the mobile bed gasification reactor, is also transported by means of quantification here.
[0021] The solid low temperature heat carrier assembled together with the solid product generated from pyrolysis is rapidly fluidized and lifted by hot air. During the lifting process, the carbon residue from the solid product and the carbon deposit on the surface of the solid heat carrier are burned, and the solid heat carrier is heated by the heat generated. In order to allow the carbon residue of the solid product (ie fuels in the solid pyrolysis product) and the carbon deposit in the solid heat carrier to be burned in the combustion reactor and riser, the temperature of the air fed into the admission of the combustion reactor and riser must be greater than the flammable point of the carbon residue and the carbon deposit in the solid product; normally, the temperature is higher than 400 ° C. In order to ensure the regeneration of the solid heat carrier which is used as a heating medium to meet the heat requirement of the pyrolysis reaction device and the gasification reaction device, when the solid heat carrier exits the combustion reactor and riser, the temperature must be high enough, which should normally reach 800 to 1,000 ° C, and the upper temperature limit must be less than the melting temperature of the ash from the solid product generated from pyrolysis. In order to ensure the regeneration of the solid heat carrier that is used as a catalyst, the carbon deposit on the solid heat carrier needs to be burnt out completely. In order to achieve the objective, in addition to meeting the combustion conditions of the combustion reactor and riser (such as temperature, oxygen concentration, residence time of the solid heat carrier and so on), the quantity and type of carbon deposit attached to the solid heat carrier fed to the combustion reactor and riser pipe must be controlled, for example, by controlling the appropriate residence time of the solid heat carrier in the mobile bed gasification device. In the situation where the operating condition of the combustion reactor and riser cannot meet the requirements for full combustion of the carbon deposit in the solid heat carrier catalyst, a special carbon-burning regenerator must be arranged before the device for pyrolysis reaction and the moving bed gasification device, to ensure that the solid catalyst heat carrier does not have any carbon deposits during circulation back to the pyrolysis reaction device and the moving bed gasification device .
[0022] In the circumstances of fluidization and high temperature of the combustion reactor and riser pipe, the solid heat carrier particle will inevitably be worn. Therefore, solid heat carrier particles with good mechanical resistance at high temperatures must be employed and, at the same time, the solid heat carrier must be replenished in time by refilling the intake of solid heat carrier arranged in the combustion reactor and riser.
[0023] An auxiliary fuel can be added through the auxiliary fuel intake, which is arranged at the bottom of the combustion reactor and riser, to supplement heat by combustion, if the solid product generated from the pyrolysis of the materials solid organic raw materials have a low carbon residue yield, so the combustion of the carbon residue from the solid product in the combustion reactor and riser is not sufficient to provide the desired heat of the reaction system. A gaseous, liquid or solid fuel can be used as the auxiliary fuel. Auxiliary fuel fed from the bottom of the combustion reactor and riser can also be used for ignition and starting operations of the reaction system
[0024] To solve the problem in which the solid product generated from pyrolysis of the solid organic raw material has a low carbon residue yield, so that the combustion of the carbon residue from the solid product in the combustion reactor and pipe ascending is not sufficient to supply the desired heat of the reaction system, another efficient way is to use cogaseification, that is, some solid product generated from pyrolysis with a high carbon residue yield (such as petroleum coke) is added to the solid organic raw materials to be fed to the pyrolysis reaction device, to provide a mixed raw material. The solid product generated from pyrolysis of the mixed raw material must have a sufficiently high carbon residue yield, so that the combustion of that solid product has the capacity to supply the heat to the reaction system. In comparison with direct combustion of an auxiliary fuel in the combustion reactor and riser, the advantage of this method is that the hydrogen-rich compositions of the raw materials can be transported to the product during the copyrolysis process, instead of being burned directly.
[0025] Size classification and dust removal operations for the solid heat carrier include: a high temperature solid heat carrier that has been heated in the combustion reactor and riser, together with a hot combustion gas, enters the dedusting device for classification of solid heat carrier in which the solid heat carrier, which is used as a moving particle filter material, is regenerated by removing dust. Based on the difference in flow rate of the solid heat carrier that drags the fed dust to the dedusting device for classification of solid heat carrier, using the difference in density, inertia force or centrifugal force, or the combination of two or three of these between solid particles with different sizes, the solid heat carrier can be separated from the hot flue-laden flue gas and divided into two parts, each with a smaller or larger average particle size. After leaving the dedusting device for classification of solid heat transporter, the dust-laden hot combustion gas is emitted after being subjected to dust removal and thermal recycling. As a heat medium, each of the two parts of the solid heat carrier with small and large average particle size is fed to the pyrolysis reaction device and the gasification reaction device, respectively, for a new operating cycle, so forming the said cycle. The classification of the solid heat carrier particle can also be achieved by the mechanical screening method.
[0026] The function of the solid heat carrier particle classification is: as a heating medium in the pyrolysis reaction device, the small particle solid heat carrier has a larger specific surface area and it is easier to achieve a mixture and rapid heating with solid organic raw materials at a lower mixing ratio, so that the organic matter in the solid organic raw materials can be completely converted into a gaseous product, and in addition to a hydrogen rich gas through steam gasification . As a heating medium, catalyst and moving particle filter material in the moving bed gasification device, the solid heat carrier particle with a larger average particle size is advantageous for reducing resistance when the gaseous product generated from pyrolysis flows through the mobile particle layer of the solid heat carrier, and it is advantageous for the heterogeneous catalytic gasification of gas / solid to be carried out without difficulty, and at the same time, capture the dust entrained in the gaseous product generated from pyrolysis.
[0027] It is possible to observe that the method of the invention includes two parallel circulations of the solid heat carrier:
[0028] 1. The circulation of the solid heat carrier used to heat the solid organic raw material to achieve rapid pyrolysis:
[0029] While it is separated from the dust-laden hot combustion gas in the dedusting device for classification of the solid heat conveyor, the high temperature solid heat conveyor of the combustion reactor and riser is divided into two parts according to difference in average particle size. As a heating medium, the solid heat carrier with smaller average particle size is mixed with solid organic raw materials in the pyrolysis reaction device so that the solid organic raw materials are heated to be pyrolyzed. Then, the low temperature solid heat carrier, whose temperature is lowered due to the supply of heat to heat the solid organic raw materials, is mixed with the solid heat carrier from the gasification reaction device; the mixture is heated to a high temperature by the combustion reactor and riser pipe and raised to be fed to the dedusting device for classification of solid heat transporter, to start another circulation.
[0030] 2. The circulation of the solid heat carrier used as a heating medium, catalyst and moving particle filter material simultaneously:
[0031] While it is separated from the dust-laden hot flue gas in the dedusting device for classification of solid heat carrier, the high temperature solid heat carrier from the combustion reactor and riser is divided into two parts according with the difference of the average particle size. The solid heat carrier with a larger average particle size enters the mobile bed gasification device and heats the gaseous product from the pyrolysis reaction device to allow pyrolysis and catalytic vapor gasification to occur. At the same time, the dust entrained in the gaseous product from the pyrolysis reaction device is captured by the particle layer of the solid heat carrier. Then the solid heat carrier with decreased temperature and captured dust enters the combustion reactor and riser and is mixed with the solid heat carrier and the solid product from the pyrolysis reaction device to provide a mixture, and the The mixture is then heated and raised. During the heating and lifting process, the carbon deposit on the surface of the solid heat carrier is burned, and through this burning the solid heat carrier used as a catalyst is regenerated. Then, the high temperature solid heat carrier returns to the dedusting device for solid heat carrier classification to start another circulation.
[0032] In the previous method, annealed olivine exhibits relatively good abrasion resistance and high temperature, and has a catalyst activity for gasification with tar and low carbon hydrocarbon. Therefore, annealed olivine is the basic solid heat carrier for the present invention. Solid heat carriers suitable for the present invention further include silica sand, corundum sand, calcined magnesite, high temperature ceramic materials, mullite, zircon sand, iron sand, solid generated from pyrolysis of raw materials (ie, the solid product generated from pyrolysis of raw materials can also be used in a circular manner as a solid heat carrier) or combinations of two or more of these
[0033] In the previous method, the preferred embodiment of the solid heat carrier is a solid heat resistant catalyst that has a catalyst activity for the decomposition / conversion reaction involved with vapor of the gaseous product generated from pyrolysis, which can be olive, or nickel-based catalyst with olivine support, or iron-based catalyst with olivine support, or nickel-based perovskite catalyst, or commercial nickel-based catalyst or combinations thereof.
[0034] In the previous method, limestone, dolomite or calcite can be used together with the solid heat carrier to function as a desulfurizer, carbon dioxide adsorbent and solid heat carrier. This is advantageous for both decomposition involved with steam and conversion of tar and low carbon hydrocarbon, as well as for desulphurizing and improving the hydrogen content of the gas product. Considering the case of limestone that is added as an example, at the high temperature of the combustion reactor and rising pipe the limestone is decomposed to provide calcium oxide. Calcium oxide, which is circulated back to the pyrolysis reaction device, is used not only as a heat carrier to provide the heat required for the pyrolysis of solid organic matter but is also used as a desulphurizer to react with the sulfide of hydrogen generated from the pyrolysis process and to take the generated sulfur into the combustion reactor and riser pipe, which can prevent the generated sulfur from entering the mobile bed gasification device and from additionally entering the gas product gas. The sulfur that enters the mobile bed gasification device will deactivate the nickel-based catalyst. The calcium oxide, which is circulated back to the pyrolysis reaction device and the moving bed gasification device, can be used as a carbon dioxide adsorbent to react with the carbon dioxide entrained in the gaseous pyrolysis product. generate calcium carbonate. This reaction can promote the water / gas conversion reaction, thus improving the hydrogen content of the product gas. At the same time, the reaction is an exothermic reaction, which is therefore advantageous for improving the thermal balance of the reaction system. However, when carried out at atmospheric pressure and at a relatively low temperature, the reaction is thermodynamically efficient. Therefore, the reaction occurs mainly in the pyrolysis reaction device with a relatively low temperature. In order to promote the reaction that occurs in the mobile bed gasification device, the temperature of the mobile bed gasification device must be controlled at a relatively low temperature, for example, 700 to 750 ° C.
[0035] The determination of the upper particle limit of the previous solid heat transporter depends on the possibility of it being raised without difficulties in the combustion reactor and riser. Normally, the upper particle limit of the previous solid heat carrier is controlled below 6 mm.
[0036] In the previous method, the operating pressure of each reactor is the atmospheric pressure; the temperature of the pyrolysis reaction device is 400 to 800 ° C, the temperature of the mobile bed gasification reaction is 700 to 950 ° C and the temperature of the combustion reactor and riser is 800 to 1,100 ° Ç.
[0037] The present invention also provides a system for the preparation of a gas rich in hydrogen through gasification with vapor of solid organic raw materials. The system consists of the following parts: dedusting device for classification of solid heat conveyor 1, pyrolysis reactor 2, mobile bed gasification reactor 3, combustion reactor and riser tube 4, condensation cooling system 5 and so on . For circulations of solid heat transporters, the pyrolysis reactor 2 and the mobile bed gasification reactor 3 are arranged in parallel. That is, after leaving the dedusting device for classification of solid heat carrier 1, a part of the solid heat carrier enters the pyrolysis reactor 2 and the other part enters the mobile bed gasification reactor 3.
[0038] In the present invention, the pyrolysis reactor is selected from a moving bed pyrolysis reactor and a fluidized bed pyrolysis reactor, preferably a moving bed pyrolysis reactor. A combustion reactor and riser can be used in correspondence with a combination of a pyrolysis reactor and a mobile bed gasification reactor, which are arranged in parallel, and the gaseous product generated from the pyrolysis reaction is fed to the mobile bed gasification reactor. Regarding the lack of correspondence between the combustion reactor and riser tube and the combination of pyrolysis reactor and mobile bed gasification reactor, specifically, the production capacity of the combustion reactor and riser tube is relatively high, while the capacity of processing and volume of the individual reactor of both the pyrolysis reactor and the mobile bed gasification reactor is relatively low; the following ways can preferably be employed in the rapid pyrolysis method of the present invention to improve the production capacity of the single system: a combustion reactor and riser is used in combination with two or more pyrolysis reactors (as shown in Figure 3, two pyrolysis reactors 21, 22 which are arranged in parallel), in which the mixtures between the vapor and the gaseous pyrolysis product that drags dust from all the parallel pyrolysis reactors are joined and fed to a bed gasification reactor common mobile. Or, otherwise, a combustion reactor and riser is used in combination with a combination of two or more parallel pyrolysis reactors and two or more parallel moving bed gasification reactors, where each pyrolysis reactor corresponds to one or more more mobile bed gasification reactors, or each mobile bed gasification reactor corresponds to one or more pyrolysis reactors, and the gaseous pyrolysis product generated from the pyrolysis reactor is respectively fed into a corresponding mobile bed gasification reactor .
[0039] The dedusting device for the classification of solid heat carrier 1 has an inlet to feed the mixture of solid heat carrier particle and flue gas that drags dust and an outlet to discharge flue gas loaded with dust in the upper portion , and a small particle solid heat carrier outlet and a large particle solid heat carrier outlet at the bottom. The small and large particle solid heat carrier outlets, respectively, provide access to the pyrolysis reactor 2 and the mobile bed gasification reactor 3 arranged under the dedusting device for classification of solid heat carrier.
[0040] The moving bed pyrolysis reactor 2 includes two parts, which are a pre-mix or integrated section and a reaction section. The solid organic raw materials and the small particle solid heat carrier from the dedusting device for solid heat carrier classification 1, respectively, are fed to the mixing section of the moving bed pyrolysis reactor and then fed to the reaction section after being thoroughly mixed. The moving bed pyrolysis reactor has an outlet at the bottom end, which is used to feed the mixture of solid heat carrier and solid pyrolysis product to the combustion reactor and riser tube 4. The moving bed pyrolysis reactor has a exit of gaseous product in the upper portion which is connected to the mobile bed gasification reactor 3 to provide an access to feed the mixture of gaseous and steam pyrolysis product to the mobile bed gasification reactor. A steam inlet is also arranged at the bottom of the moving bed pyrolysis reactor. A mechanism for detecting and controlling the level of solid material is provided in the moving bed pyrolysis reactor to maintain the level of solid material in the pyrolysis reaction section below the outlet to discharge the gaseous product generated from pyrolysis.
[0041] The upper inlet of the mobile bed gasification reactor 3 is connected to the large particle solid heat carrier outlet of the dedusting device for the classification of solid heat carrier 1, and the lower outlet of the mobile bed gasification reactor. is connected to the bottom of the combustion reactor and riser tube 4. An inlet to feed the mixture of gaseous pyrolysis product that entrains dust and steam and an outlet to discharge the gasification product with steam are arranged in the bed gasification reactor mobile, and are respectively connected to the mobile bed pyrolysis reactor 2 and to the condensation cooling system 5.
[0042] The combustion reactor and riser 4 at the bottom is equipped with a hot air inlet, an inlet for mixing solid heat carrier from the pyrolysis reactor and solid product, and an inlet for air carrier solid heat from the mobile bed gasification reactor that already captures dust. An additional intake to refill solid heat carrier and auxiliary fuel is provided at the bottom of the combustion reactor and riser. The top outlet of the combustion reactor and riser pipe is connected to the dedusting device for classification of solid heat transporter.
[0043] Special carbon burning regenerators 6 and 7 can be respectively arranged between the dedusting device for classification of solid heat transporter 1 and the moving bed pyrolysis reactor 2, and between the dedusting device for classification of conveyor of solid heat. solid heat 1 and the mobile bed gasification reactor 3. The mobile bed reactor or the fluidized bed reactor can be used as the carbon burning regenerator.
[0044] With the aid of the material sealing effect caused by the solid heat transporter in the pipes connecting adjacent reactors, the atmosphere in the mobile bed pyrolysis reactor and the mobile bed gasification reactor, the atmosphere in the dedusting device for classification of solid heat transporter located above and the combustion reactor atmosphere and riser pipe located below are disconnected from each other, and there is no leakage between them. Therefore, a hydrogen-rich gas product with almost no nitrogen can be achieved.
[0045] The operating pressure of each of the previous reactors is the atmospheric pressure.
[0046] Compared with the prior art, the main technical effects and technical resources that can be achieved by the method of the previous invention for the preparation of a hydrogen-rich gas through vapor gasification of solid organic raw materials are:
[0047] The method provided by the present invention includes two parallel solid heat carrier circulations, each of which can be independently optimized and controlled, in which the circulated solid heat carrier is divided into two parts, each with a different average particle size. The part with the smallest particle size is used as a heating medium to heat a solid organic raw material, which is therefore rapidly pyrolyzed; and the other part with a larger particle size is used as a heating medium, catalyst and moving particle filter material for gasification with catalytic vapor of gaseous product which includes tar and low carbon hydrocarbon generated from pyrolysis and which captures dust entrained in the gaseous product generated from pyrolysis.
[0048] With the aid of the circulation of solid heat transporters, the combustion reactor and riser can be connected in tandem to the parallel bed pyrolysis reactor and the parallel bed gasification reactor, respectively, in order to combine the three in a gasification system. The method achieves respective independent control over (1) the pyrolysis of the solid organic raw material, (2) the decomposition and conversion involved with steam (also known as gasification) of the gaseous product (which includes tar and hydrocarbon gas) generated at from pyrolysis and (3) independent control of the combustion reaction of the solid product generated from pyrolysis that provides the heat required for the pyrolysis of raw material and the decomposition and conversion involved with steam of the pyrolysis gas product. The method has a simple process and an operation at normal pressure and thus is suitable for gasification and co-gasification is several highly volatile solid organic materials, including raw materials that contain a relatively large amount of moisture, mineral substance and sulfur .
[0049] The circulated solid heat carrier is subjected to a size classification and allocated to the moving bed pyrolysis reactor and the moving bed gasification reactor which are arranged in parallel, with which the optimization of operating conditions both the mobile bed pyrolysis reactor and the mobile bed gasification reactor can be achieved. That is, the solid heat carrier with small particle size is applied to the pyrolysis reactor to achieve rapid pyrolysis of raw materials. Meanwhile, the larger particle size solid heat carrier is applied to the moving bed gasification reactor, which allows the moving bed gasification reactor to have a lower bed layer resistance and achieve greater efficiency in decomposition and conversion of tar and low carbon hydrocarbon and in the removal of hot dust, with the assumption of an adequate catalyzing gasification effect. As such, the conversion of organic substances in the solid organic raw material into a hydrogen-rich gas, a clean target product, can be maximized.
[0050] Using highly volatile raw materials in combination with raw materials that will achieve a relatively high yield of solid product generated from pyrolysis that has a high carbon content, that is, using a co-gasification method, a solid product with the desired quantity and carbon residue content can be generated from pyrolysis, with which it is possible to supply the heat required to the reaction system through the combustion of said solid product, so that an energy balance of the reaction can be achieved without external heat supply. Since there is no need to directly burn solid organic raw materials for heat supply, a targeted transfer of hydrogen from raw materials to the product, a hydrogen-rich gas, can be maximized.
[0051] After being connected in parallel, the multiple mobile bed pyrolysis reactors and the corresponding mobile bed gasification reactors are connected to the combustion reactor and tandem riser. With this, the production capacity of the system can be improved efficiently and the limitation of the low production capacity of the individual mobile bed pyrolysis reactor can be overcome. DESCRIPTION OF THE DRAWINGS
[0052] Figure 1 is a schematic diagram showing the principle of operation of the method provided by the present invention for the preparation of a gas rich in hydrogen through the gasification with vapor of solid organic raw materials;
[0053] Figure 2 is a schematic diagram showing the principle of operation of the method provided by the present invention for the preparation of a gas rich in hydrogen through the gasification with vapor of solid organic raw materials (including a burner regenerator) of carbon);
[0054] Figure 3 is a schematic diagram showing the system that has parallel moving bed pyrolysis reactors and used to implement the method of the present invention for the preparation of a gas rich in hydrogen through gasification with raw materials steam solid organic;
[0055] DETAILED MODALITIES
[0056] The technical solution in the present invention will be further illustrated below with reference to the specific Figures and modalities.
[0057] The rapid cogaseification of white and lignite pine chips is carried out in the experiment system with a processing scale of 1 kg / h, and the principle of operation of this experiment system is the same as that shown in Figure 1. The humidity in based on dry air, the volatile matter on a dry air basis and the particle size of the white pine chips of the first raw material and the lignite of the second raw material are respectively 5.0%, 77.7%, less than 2 mm and 27.9%, 35.1%, less than 1.2 mm. Before the experiment, the raw materials are dried for an hour at a temperature of 105 to 110 ° C in the oven. Olivine or nickel-based catalyst particles with olivine support with a particle size of 0.2 to 1.2 mm are used as a circulating solid heat carrier.
[0058] After drying, the chips of white pine and lignite are respectively fed by quantification to a secondary screw feeder from each raw material storage tank through corresponding primary screw feeders; both materials are fed at a feed rate of 250 g / h. The mixture of white pine and lignite chips is quickly transported and fed from the secondary screw feeder to an internally disposed stirring mixer located in the upper portion of the moving bed pyrolysis reactor 2. Then the mixture is quickly mixed with a high temperature circulated solid heat carrier from the dedusting device for classification of solid heat carrier 1, the most likely particle size of which is about 0.5 mm, and quickly falls into the reaction section located in the lower portion of the pyrolysis reactor in a moving bed 2 to carry out the pyrolysis reaction.
[0059] The level of solid material of the moving bed pyrolysis reactor 2 is measured with an obstruction level probe. The flow of solid heat carrier fed to the pyrolysis reactor is controlled by a valve that connects the dedusting device for classification of solid heat carrier 1 and the moving bed pyrolysis reactor 2; the flow of the mixture of the solid heat carrier leaving the pyrolysis reactor and the solid product generated from pyrolysis is controlled by a valve configured in the pipeline that connects the pyrolysis reactor 2 and the bottom of the combustion reactor and riser tube 4 ; through the cooperation of the two previous valves, the level of solid material of the pyrolysis reactor can be controlled to about 20 mm below the pyrolysis gas outlet.
[0060] An overheated steam inlet is disposed in the lower portion of the moving bed pyrolysis reactor 2. The superheated steam fed to the moving bed pyrolysis reactor 2 with an overheating temperature of 450 ° C passes through the layer comprising the solid heat carrier and the solid product generated from pyrolysis, and rises. During this process, the steam is further heated by the solid product generated from pyrolysis and the solid heat carrier, and at the same time, the gaseous product generated from pyrolysis is transported and leaves the solid material layer of the pyrolysis reactor. moving bed together with steam.
[0061] The gaseous product of the pyrolysis of the raw materials in the mobile bed pyrolysis reactor is fed to the mobile bed gasification reactor 3 under the pumping effect of a vacuum pump which is disposed downstream of the condensation cooling system. 5. The mixture of the solid product generated from the pyrolysis of raw materials in the pyrolysis reactor 2 and the solid heat carrier is fed through quantification to the mixing and pre-fluidization section at the bottom of the combustion reactor and riser pipe 4 through the pipe valve under the effect of gravity.
[0062] The mobile bed gasification reactor 3 is a radial mobile bed, within which a passage of a particle layer of a movable solid heat carrier is formed which is formed by an external network and an internal surrounding network. A central distribution gas passage is within the internal network and a union gas passage is between the external network and the external wall of the mobile bed gasification reactor 3. The high temperature circulated solid heat carrier from the device dedusting device for classification of solid heat carrier 1 with the most likely particle size of about 0.7 mm flows continuously through the passage of a circined moving particle layer, the amount of flow and dwell time of which can be controlled by the tubing connecting the mobile bed gasification reactor 3 and the bottom of the combustion reactor and riser tube 4. The gaseous product generated from pyrolysis enters the central distribution gas passage of the mobile bed gasification reactor 3 from the upper portion of it. After passing through the mobile particle layer of a solid heat conveyor in a cross-flow mode, the gaseous product is collected in the union gas passage and fed to the condensation cooling system 5 through the gas outlet pipe located in the upper portion of the reactor in moving bed 3.
[0063] The condensation cooling system 5 is in an indirect condensation cooling mode and includes two circulated chilled water condenser sections and two low temperature (-10 ° C) chilled sections in tandem. The hot gas from the mobile bed gasification reactor 3 flows through the four previous sections of the condensation cooling reactor, in which the condensable matter (water and a small amount of tar) is condensed and collected in the liquid storage tank. at the bottom of each section of the condensation cooling reactor. After cooling, the gas is fed to a filter filled with degreasing cotton to capture the airgel or residual tar fog, and then the gas is fed to a gasometer via a vacuum pump.
[0064] The mixture of the solid heat carrier from the mobile bed pyrolysis reactor 2 and the solid product generated from the pyrolysis is joined to the solid heat carrier from the mobile bed gasification reactor 3 in the pre section -fluidization at the bottom of the combustion reactor and riser 4. The schematic diagram of the structure of the pre-fluidization section at the bottom of the combustion reactor and riser 4 is shown in Figure 3. In addition to the main air lift function, a second air intake is arranged to assist the pre-fluidization of the solid material.
[0065] The temperature of the hot air fed to the bottom of the combustion reactor and riser 4 is controlled at 400 ° C. During the process of lifting the mixture of the solid heat carrier and the solid product generated from pyrolysis by hot air, the carbon residue in the solid product generated from pyrolysis and the carbon deposit attached to the solid heat carrier are burned completely and, at the same time, the solid heat carrier is heated. Then, the high temperature solid heat carrier, together with the hot flue gas laden with gas dust, exits the upper portion of the combustion reactor and riser 4 and is fed to the dedusting device for heat carrier classification solid 1.
[0066] The dedusting device for classification of solid heat carrier 1 consists of internal and external cylinders that have a conical shape at the bottom, and each has a solid heat carrier outlet at the bottom of it. The outlets for the solid heat transporter lead respectively to the moving bed pyrolysis reactor 2 and the moving bed gasification reactor 3. The inner cylinder has a height of about 1/3 to 2/3 the height of the outer cylinder, and is opened at the top end. The upper end of the outer cylinder is closed and has an outlet for hot flue gas loaded with dust arranged in the central portion of it. An inlet for the mixture of hot flue gas and high temperature solid heat carrier is in the horizontal tangent direction of the inner wall of the outer cylinder at the top of the dedusting device for classification of solid heat carrier 1.
[0067] After the entry of the hot flue gas carrying a high temperature solid heat carrier along the tangent direction of the combustion reactor and riser 4 to the dedusting device for classification of solid heat carrier 1, under the effect of inertial force and centrifugal force, the solid heat carrier with larger average particle size falls mainly in the conical shape section at the bottom of the outer cylinder, and the solid heat carrier with smaller average particle size falls mainly in the section conical in shape at the bottom of the inner cylinder, while fine dust, together with the hot flue gas, comes out of the hot flue gas outlet at the upper end and is emitted after additional dust removal and cooling.
[0068] Table 1 shows the results of two experiments, which use, respectively, calcined olivine and nickel with calcined olivine support at 900 ° C (the mass fraction of NiO is 5%) as the circulated solid heat carrier , and chips of white pine and lignite are fed continuously for 3 hours. Other experimental conditions are: the circulation rate of the solid heat transporter that passes through the pyrolysis reactor in a moving bed is 2 kg / h; the circulation rate of the solid heat transporter that passes through the gasification reactor in a radial moving bed is 3 kg / h; the temperature of the combustion reactor and riser pipe is 870 ° C; the dedusting device temperature for classification of solid heat transporter is 870 ° C; the temperature of the moving bed pyrolysis reactor is 600 ° C; the temperature of the gasification reactor in a radial moving bed is 850 ° C; the mass to steam ratio (lignite + white pine chips) is 0.64. After being collected through a gasometer, the product rich in hydrogen gas is subjected to composition and content analysis with gas chromatography. The method for analyzing liquid product is shown below: after the experiment, tetrahydrofuran (THF) is used to wash the condensation cooling system and collect a liquid product. The collected liquid mixture (water + tar + THF) is evaporated by a rotary evaporator at 40 ° C and under reduced pressure, which is to remove the THF to obtain the mixture of tar and water; ethyl acetate is used to extract the tar, and the mixture of ethyl acetate and tar is evaporated through a rotary evaporator at 45 ° C and under reduced pressure, which is to remove the ethyl acetate to obtain tar, and then the amount of tar and water is measured and calculated.
[0069] The result of the experiment shows that, as compared with calcined olivine, as the circulated solid heat carrier, the nickel catalyst with calcined olivine support exhibits a relatively high activity in removing tar and reforming methane from the gaseous product, and the gas yield and the H2 and CO content of the product gas are improved, in which the tar decomposition / removal rate and the methane conversion rate are 94.4% and 98.2%, respectively. Within the collected liquid product, no significant amount of dust is detected. TABLE 1 COMPARISON OF GASIFICATION CAPACITY OF DIFFERENT SOLID HEAT TRANSPORTERS CATALYST

权利要求:
Claims (15)
[0001]
1. Method for preparing a gas rich in hydrogen from solid organic materials characterized by comprising: heating the solid organic raw materials in a pyrolysis reaction device to allow pyrolysis to occur; and gasifying a gaseous product and steam in a mobile bed gasification device to generate a hydrogen rich gas, in which the gaseous product is generated from pyrolysis; wherein the pyrolysis reaction device is parallel to the mobile bed gasification device; passing through a dedusting device for classification of solid heat carrier, the solid heat carrier is divided into two parts which are fed, respectively, to the pyrolysis reaction device and the mobile bed gasification device, and during the exit of the pyrolysis reaction device and the mobile bed gasification reaction the two parts of the solid heat carrier are fed into a combustion reactor and riser to be heated and lifted, and are then passed back to the interior of the dedusting device for classification of solid heat carrier to be divided into two parts, and these two parts are then fed back to the pyrolysis reaction device and the mobile bed gasification device, respectively, to create a cycle; wherein the part of the solid heat carrier that is fed to the pyrolysis reaction device is used as a heating medium for pyrolysis and the other part of the solid heat carrier that is fed to the moving bed gasification device is used as a heating medium for gasification, and where the dedusting device for classification of solid heat carrier divides the solid heat carrier into two parts based on the average particle size, the part having an average particle size a smaller one is fed to the pyrolysis reaction device and the other part with a larger average particle size is fed to the mobile bed gasification device.
[0002]
2. Method, according to claim 1, characterized in that: (i) the solid organic raw materials are selected from biomass, polymeric solid waste, coal, petroleum coke or combinations of two or more of these, optionally by the biomass consists of the components of cellulose, hemicellulose, lignin and the like, which comprises agricultural manure, forestry manure or energy culture, or combinations thereof; or (ii) the pyrolysis reaction device comprises a pyrolysis reactor, or at least two parallel pyrolysis reactors, and the mobile bed gasification device comprises a mobile bed gasification reactor or at least two gasification reactors parallel moving bed; wherein each pyrolysis reactor corresponds to at least one mobile bed gasification reactor, or each mobile bed gasification reactor corresponds to at least one pyrolysis reactor; wherein the gaseous product from each of the pyrolysis reactors is fed to the corresponding mobile bed gasification reactor; or (iii) the pyrolysis reaction device comprises a fluidized bed pyrolysis reactor; or (iv) the pyrolysis reaction device comprises a moving bed pyrolysis reactor; (v) the solid heat carrier is used as a catalyst for gasification, while being used as the heating medium for gasification; or (vi) calcium oxide is used as a carbon dioxide absorber, desulfurizer and solid heat carrier for gasification, and gasification is carried out at a temperature of 700 to 750 ° C to prepare a gaseous product with a high concentration of hydrogen; or (vii) the vapor for gasification is fed from the lower portion of the layer of solid material in the pyrolysis reaction device; or (viii) the solid heat carrier in the mobile bed gasification device is used as a particle filter material while being used as a heating medium in order to capture the dust entrained in the gaseous product pyrolysis.
[0003]
Method according to claim 2, characterized in that the solid heat carrier is used as a catalyst for gasification, while being used as the heating medium for gasification, and in addition for the solid heat carrier be olivine, nickel-based catalyst with olivine support, iron-based catalyst with olivine support, nickel-based perovskite catalyst, commercial nickel-based catalyst, solid product generated from pyrolysis of organic raw materials solids or combinations of two or more of these.
[0004]
4. Method according to claim 1, characterized in that: (i) volatile matter of dry ash-free base in solid organic raw materials is presented in a mass fraction between 20 to 70%; or (ii) the temperature of the pyrolysis reaction device is adjusted by controlling the mixing ratio between the solid heat carrier and the solid organic raw materials, in order to control the degree of pyrolysis of the solid organic raw materials; or (iii) in unit of time, the mass ratio between the solid heat carrier fed to the pyrolysis reaction device and the solid organic raw materials is 2 to 7: 1; or (iv) in unit of time, the mass ratio between the solid heat carrier fed to the pyrolysis reaction device and the solid organic raw materials is 3 to 5: 1; or (v) the particle size of the solid organic raw materials is up to 8 mm; or (vi) the particle size of the solid organic raw materials is less than 3 mm; or (vii) the temperature of the pyrolysis reaction device is 400 to 800 ° C; or (viii) the temperature of the pyrolysis reaction device is 500 to 700 ° C; or (ix) the temperature of the mobile bed gasification reaction is 700 to 950 ° C; or (x) the temperature of the mobile bed gasification device is 800 to 950 ° C; or (xi) the temperature at which the gasification is carried out is adjusted by controlling the temperature and the circulation rate of the solid heat carrier that is fed to the mobile bed gasification device; or (xii) the particles of the solid heat carrier form a moving layer in the moving bed gasification device.
[0005]
Method according to claim 4, characterized in that the particles of the solid heat carrier form a movable layer in the device for gasification reaction in a moving bed and also the mixture between the gaseous product generated from pyrolysis in the device for pyrolysis reaction and steam contacting the moving layer in a contact mode selected from a group consisting of parallel current, counter current, radically crossed current or combinations of the flow and gas / solid contact mode above; optionally but when an iron-based or nickel-based catalyst is used as the solid heat carrier, the mixture between the gaseous products generated from pyrolysis and the steam comes into contact with the moving layer in a contact mode countercurrent or radically crossed current.
[0006]
6. Method according to claim 1, characterized in that the combustion reactor and riser pipe is provided with a hot air inlet, and in which: (i) the inlet temperature of the hot air entering the combustion reactor and riser pipe is configured to guarantee the combustion of the carbon residue and the carbon deposit; or (ii) the inlet temperature of the hot air is greater than 400 ° C.
[0007]
7. Method according to claim 6, characterized by: a secondary reaction of the gaseous product generated from the pyrolysis of the solid organic raw materials occurs in the pyrolysis reaction device to form a carbon deposit on the surface of the heat carrier solid; the solid product generated from pyrolysis during the exit of the pyrolysis reaction device forms a mixture with the solid heat carrier that carries the carbon deposit, and the mixture is joined to the solid heat carrier at the outlet of the device for reaction of mobile bed gasification with dust captured in the combustion reactor and riser pipe and is quickly fluidized and lifted by hot air; during lifting, the carbon residue in the solid product generated from pyrolysis and the carbon deposit are burned to provide heat, so that the solid heat carrier is heated and regenerated.
[0008]
Method according to claim 1, characterized in that: (i) the solid heat carrier is heated to a temperature between 800 and 1,100 ° C in the combustion reactor and riser; or (ii) in the combustion reactor and riser, the solid heat carrier has a temperature lower than the melting temperature of the ash content of the solid product generated from pyrolysis; or (iii) an inlet to refill the solid heat carrier is configured in the lower portion of the combustion reactor and riser; or (iv) an inlet to refill the auxiliary fuel is configured in the lower portion of the combustion reactor and riser, and the auxiliary fuel is used for one or both of the following purposes: (1) the auxiliary fuel is used for ignition operations and starting the entire system; (2) auxiliary fuel is burned to replenish heat if the solid product generated from the pyrolysis of solid organic raw materials has a low carbon residue yield, so that the combustion of the carbon residue in the combustion reactor and pipe upward is not sufficient to provide the desired heat.
[0009]
Method according to claim 1, characterized in that: (i) the carbon deposit and the solid product comprising carbon residue are generated from the pyrolysis of the solid organic materials; the carbon residue and the carbon deposit are then burned in the combustion reactor and riser pipe to provide heat for pyrolysis and gasification; or (ii) the solid heat carrier is separated from the dust-laden hot combustion gas in the dedusting device for solid heat carrier classification and is divided into two parts, where one part has a smaller average particle size and the another part has a larger average particle size; the separation is performed based on the difference in flow rate of the dust-laden solid heat carrier due to the difference in density, inertia force or centrifugal force of the solid particles with different particle sizes, or combinations of two or three of the above characteristic differences ; or (iii) a particle size classification of the solid heat carrier in the dedusting device for solid heat carrier classification is carried out by means of mechanical sieving; or (iv) the solid heat carrier is olivine particles, silica sand, corundum sand, calcined magnesite, high temperature ceramic materials, mullite, zircon sand, iron sand, solid product generated from pyrolysis of the materials - solid organic raw materials or combinations of two or more of these; or (v) the solid particulate heat carrier has a particle size of up to 6 mm; or (vi) the operating pressure for each reactor and reaction device is atmospheric pressure; or (vii) in unit of time, the mass ratio between the solid heat carrier entering the mobile bed gasification reaction and the solid heat carrier entering the pyrolysis reaction device is controlled in the range of 0 , 5 to 5.
[0010]
Method according to claim 9, characterized in that the solid product and the carbon deposit comprise carbon residue are generated from the pyrolysis of the solid organics, the carbon residue and the carbon deposit are burned in the combustion reactor and riser to provide heat for pyrolysis and gasification and if pyrolysis generates the carbon residue in low yield, so that combustion of the carbon residue in the combustion reactor and riser is not sufficient to provide the desired heat for pyrolysis and gasification , then the components of the solid organic raw materials fed to the pyrolysis reaction device, which can generate a solid product with higher carbon residue yield, will be added, or other solid organic raw materials which can generate a solid product with higher carbon residue yield through pyrolysis will be added, in order to increase carbon residue yield in the solid pyrolysis product to provide sufficient heat, and optionally yet another solid organic raw material that can generate a solid product with a higher yield of carbon residue through pyrolysis being petroleum coke.
[0011]
11. System for the preparation of a gas rich in hydrogen from solid organic materials characterized by comprising: a dedusting device for the classification of a solid heat carrier, to divide the solid heat carrier into two parts, in which one part it has a smaller average particle size and the other part has a larger average particle size; a pyrolysis reaction device for heating the solid organic matter with the smaller medium particle size solid heat carrier from the dedusting device for solid heat carrier classification, to allow pyrolysis to occur; a device for gasification reaction in mobile bed, to receive the gaseous product generated from pyrolysis in the device for pyrolysis reaction, and that allows the gasification of the gaseous product and steam to generate the hydrogen rich gas through the heat transporter solid with larger average particle size from the dedusting device for classification of solid heat carrier; and a combustion reactor and riser to receive and burn the solid heat carrier from the pyrolysis reaction device, the solid product generated from the pyrolysis and the solid heat carrier from the bed gasification device mobile, so that the solid heat carrier received by the combustion reactor and riser can be heated and raised to the dedusting device for classification of solid heat carrier.
[0012]
System according to claim 11, characterized in that the pyrolysis reaction device comprises a pyrolysis reactor or at least two parallel pyrolysis reactors, the mobile bed gasification reaction device comprises a moving bed gasification reactor or at least two parallel mobile bed gasification reactors, where each pyrolysis reactor corresponds to at least one mobile bed gasification reactor, or each mobile bed gasification reactor corresponds to at least one pyrolysis reactor; wherein the gaseous product from each of the pyrolysis reactors is fed to the corresponding mobile bed gasification reactor.
[0013]
13. The system according to claim 12, characterized in that: (i) the pyrolysis reaction device comprises a moving bed pyrolysis reactor; or (ii) the pyrolysis reaction device comprises a fluid bed pyrolysis reactor; or (iii) carbon-burning regenerators are respectively configured between the dedusting device for the classification of the solid heat carrier and the device for the pyrolysis reaction, and between the dedusting device for the classification of the solid heat carrier and the device for the reaction. mobile bed gasification; the carbon-burning regenerator is used to completely burn the carbon deposit that remains in the solid heat carrier; wherein the carbon deposit is formed on the surface of the solid heat carrier through the secondary reaction of the gaseous product generated from pyrolysis; or (iv) the mobile bed gasification device is additionally used to capture dust in the gaseous product generated from pyrolysis; or (v) the combustion reactor and riser is equipped with a hot air inlet. (vi) the temperature of entry of hot air into the combustion reactor and riser pipe is greater than 400 ° C; or (vii) further comprising a condensation cooling device, the condensation cooling device being used to condense condensable substances in the hot gaseous product from the mobile bed gasification device; the gaseous product comprises hydrogen-rich gas.
[0014]
Device according to claim 13, characterized in that the carbon-burning regenerators are respectively configured between the dedusting device for the classification of the solid heat carrier and the device for the pyrolysis reaction, and between the dedusting device for the classification of solid heat transporter and the device for gasification reaction in mobile bed; the carbon-burning regenerator is used to completely burn the carbon deposit that remains in the solid heat carrier; wherein the carbon deposit is formed on the surface of the solid heat carrier through the secondary reaction of the gaseous product generated from pyrolysis; and because the carbon-burning regenerator is either a fluidized bed reactor or a moving bed reactor.
[0015]
15. System according to claim 13, characterized in that: the solid product generated from pyrolysis leaves the device for pyrolysis reaction to form a mixture with the solid heat carrier loaded from the carbon deposit, the mixture is quickly fluidized and lifted by the hot air in the combustion reactor and riser tube together with the captured dust-laden solid heat carrier that leaves the device for mobile bed gasification reaction, and during the elevation the carbon residue contained in the solid product and the deposit carbon are burned to provide heat so that the solid heat carrier is heated and regenerated; in which the carbon deposit is formed on the surface of the solid heat carrier through the secondary reaction of the gaseous product generated from pyrolysis, and optionally because the temperature of entry of the hot air into the combustion reactor and riser pipe is configured to guarantee combustion of carbon waste and carbon deposit.

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同族专利:

公开号 | 公开日

MY180238A|2020-11-25|

AU2014295756A1|2016-02-11|

BR112016001196A2|2019-12-17|

EP3026098A1|2016-06-01|

US9809770B2|2017-11-07|

DK3026098T3|2019-01-21|

EP3026098B1|2018-10-31|

ES2707379T3|2019-04-03|

PL3026098T3|2019-06-28|

US20160186079A1|2016-06-30|

EP3026098A4|2017-01-18|

EP3026098B8|2019-01-02|

AU2014295756B2|2018-03-08|

CN103468322A|2013-12-25|

WO2015010448A1|2015-01-29|

CN103468322B|2015-08-12|

CA2918168A1|2015-01-29|

CA2918168C|2020-04-21|

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法律状态:
2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2020-02-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2020-07-21| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2020-11-10| 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 25/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

CN201310316605.7A|CN103468322B|2013-07-25|2013-07-25|A kind of method being produced hydrogen-rich gas by solid organic matters steam gasification|

CN201310316605.7|2013-07-25|

PCT/CN2014/000705|WO2015010448A1|2013-07-25|2014-07-25|Method for preparing hydrogen-rich gas by gasification of solid organic substance and steam|

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