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    • 专利摘要:
    The invention is directed to method to adapt a coal fired power plant comprising a powdered coal feed, an air feed, burners, boilers and a steam expander—generator and a flue gas stream, wherein 5 the coal feed is replaced by a powdered polymer feed and the air feed is replaced by an oxygen feed connected to an upstream air separation process resulting in a flue gas stream rich in carbon dioxide and water.
    公开号:NL2026451A
    申请号:NL2026451
    申请日:2020-09-11
    公开日:2021-05-12
    发明作者:Cramwinckel Michiel
    申请人:Cramwinckel Michiel；
    IPC主号:
    专利说明:

    METHOD TO ADAPT A COAL FIRED POWER PLANT AND PROCESS The invention is directed to a method to adapt a coal fired power plant comprising a powdered coal feed, an air feed, burners, boilers and a steam expander-generator and a flue gas stream. The invention is also directed to process to generate electricity.
    Processes to generate power, i.e. electricity, from coal are well known and probably half of the electricity generated today is generated by combustion of coal. A well-known process is where coal powder is combusted with air in a boiler furnace to produce high pressure steam and a flue gas comprising carbon dioxide, water and primarily nitrogen. The high pressure steam is expanded in a steam expander connected to a turbine (steam turbine) in which electricity is generated. The steam is condensed and reused in the steam boiler.
    A problem with such coal based power plants is that they emit carbon dioxide into the environment. Processes to capture carbon dioxide from the flue gas are known but are considered too complex to readily adapt. In some countries relatively new coal power plants are scheduled to be shut in order to comply with the more stringent carbon dioxide emission targets.
    lt is an object of the present invention to make use of the valuable hardware of the coal power plant in an application which avoids carbon dioxide emissions.
    This object is achieved by the following method. Method to adapt a coal fired power plant comprising a powdered coal feed, an air feed, burners, boilers and a steam expander-generator and a flue gas stream, wherein the coal feed is replaced by a powdered polymer feed and the air feed is replaced by an oxygen feed connected to an upstream air separation process resulting in a flue gas stream rich in carbon dioxide and water.
    The invention is also directed to a process to generate electricity by comprising the following steps: (a) combustion of powdered polymer particles with an oxygen comprising gas in a boiler to generate steam and a flue gas and, (b} expanding steam in a steam expander-generator to generate electricity.
    Applicants found that by replacing the coal feed by a powdered polymer feed a more cleaner process is obtained. The powdered polymer feed typically will contain less or even no sulphur as compared to a coal feed. This simplifies the combustion process because less measures have to be taken to remove sulphur oxides from the flue gas. Further the powdered polymer feed may comprise of waste polymers thereby providing an outlet for waste polymers, especially for waste polymers or mixtures of waste polymers which cannot be easily recycled to a reusable polymer feedstock. Further the flue gas will have a substantially higher concentration of carbon dioxide and less nitrogen oxides. Carbon dioxide can be more easily isolated from the flue gas and stored in sub surface reservoirs. Because a powdered polymer feed is used it is possible to perform the combustion such that almost only gaseous products like carbon dioxide, carbon monoxide, hydrogen and water are formed while no significant quantities of tars or liquid fuels are formed. This avoids having to upgrade such tars or liquids to a fuel suited for transportation purposes.
    Below reference to the method and process will be made. Parts discussed in the context of the method may also be used in the process and vice versa.
    The oxygen feed is connected to an upstream air separation process. Such an air separation process is preferably based on the commonly used and most well-known air separation process for oxygen and nitrogen production. This process is based on the Linde double column cycle invented In the first half of the 20™ century. The basic concept of the Linde double column cycle is to have thermal communication between the top of the higher pressure column and the bottom of the lower pressure column to condense the vapor nitrogen from the higher pressure column and reboil the liquid oxygen in the bottom of the lower pressure column. Various air separation processes have been designed based on this principle depending on the desired products. The advantage of this air separation process is that it can also produce liquid nitrogen or liquid air which can be advantageously be used in a preferred embodiment as discussed below. Alternatively the air separation process is a Pressure Swing Adsorption process wherein zeolite molecular sieves extract oxygen from air. Oxygen at 95% is delivered, while the nitrogen adsorbed by the molecular sieves is vented back into air through the exhaust line or is preferably liquified to prepare liquid nitrogen.
    In a preferred embodiment the air separation process is heat integrated with a liquified natural gas (LNG) regas plant. In this way one or more nitrogen rich gas streams of the air separation plant may be reduced in temperature and/or liquified by indirect heat exchange with the evaporating liquid natural gas of the regas plant as for example described in US5137558,
    US5139547, US5141543, US2008216512, US2008000266, US2009100863 and EP2669613. Preferably the pressure of the nitrogen rich gas streams is higher than the LNG pressure such that in case of leakage no natural gas will contaminate the nitrogen rich streams. The air separation plant preferably produces suitably both liquid nitrogen and liquid oxygen. This is especially favourable for LNG regas plants which have the function to diversify supply of methane gas to the natural gas grid as an alternative for pipeline gas. Such a regas plant may not continuously prepare the required nitrogen and/or oxygen products while the downstream processes like the cryogenic milling or the combustion process may require a constant flow of these products. By storing a buffer volume of liquid nitrogen and optionally liquid oxygen the desired constant flow may be achieved while the LNG regas plant may temporarily produce at a low production rate. This option is especially advantageous for situations where a coal fired power plant is located near a LNG regas plant as is the situation in Rotterdam Maasvlakte The powdered polymer feed is preferably a powdered polymer waste. The polymer waste may be obtained in a waste recycling process. The recycling of waste polymer products, also referred to as waste plastics, is a specific sector of waste recycling and consists of a set of operations performed on waste composed of plastic materials in order to obtain new material to be reintroduced in production processes. After the sorted waste collection step, the plastic is taken to first selection and treatment plants; it is then separated from other fractions and impurities and then divided by polymer type. in particular, low- and high-density PET and PE are selected. Various methods for mechanical recycling are known which are adapted to obtain flakes or granules which are then used to produce new objects. It is an advantage of the present process that mixtures of powdered polymers may be used as feed. This avoids complex separation steps to divide the waste polymers by polymer type.
    Because plastics cannot be recycled indefinitely and only 50% of the total of plastic waste can be reused validly in a production process the remaining 50% is not suitable for various reasons. These reasons may be for example the excessive degree of contamination of plastics, the loss of technical properties due to past recycling/reuse cycles, the impossibility to perform a selection of the various types of plastic for finer fractions. This remaining 50% of plastic waste may be advantageously used as the powdered polymer feed. The waste polymer product may be composed of thermoplastic materials and/or thermosetting materials. Preferably the polymers are polymers such as for example LDPE (Low-
    density polyethylene), HDPE (High-density polyethylene); PP (Polypropylene); PS (Polystyrene); PVC (Polyvinyl chloride); PET (Polyethylene terephthalate); PUT (Polyurethanes) and PP&A fibres {Polyphthalamide fibres). The waste polymer may be any one of the above polymers, suitably the waste polymer is a mixture comprising of at least two of the above polymers, preferably comprising of at least three of the above polymers and more preferably comprising of at least four of the above polymers. The present invention provides a method to make use of polystyrene which is difficult to recycle to its virgin state. Examples of mixtures are mixtures comprising LDPE {Low-density polyethylene) and HDPE (High-density polyethylene) and mixtures comprising LDPE (Low-density polyethylene), HDPE {High-density polyethylene) and PP (Polypropylene). Preferably polystyrene is part of the mixture. The waste polymer may also comprise any one or more of other polymers such as PMMA {polymethyl methacrylate), PVC (polyvinyl chloride}, PUR (polyurethanes), ABS (acrylonitrile- butadiene-styrene), rubbers, polyamide (Nylon).
    The waste polymers may originate from households, industry, restaurants, hospitals, retail, fishing, from contaminated seas, oceans and rivers. The waste polymer product may be contaminated by metals and biomass or biomass derived products such as paper, carton or fabrics like cotton and wool. These contaminants are preferably separated from the waste polymer product. This may be performed by first reducing the waste polymer product and its contaminants in size to obtain a mixture of smaller particles and subsequently water washing the obtained mixture. Metals may be separated by sedimentation and paper and the like by flotation. Preferably the content of these contaminants is less than 30 wt%, more preferably less than 20 wt% and more preferably less than 5 wt% and more than 0.5 wt%. The less biomass or biomass derived products are present the lower the content of ash will be present. This is advantageous because less measures have to be taken to deal with the formation of ash. Preferably clean powdered polymer feed is used because no ash will then be formed. Preferably polymers are used which do not contain sulphur. Optionally the metal contaminants may be separated from the powdered polymer particles before using them as the powdered polymer feed. Metals, like chromium, aluminium and iron may be separated by flotation or magnetic separators from the polymer particles. Exemplary waste polymer products which can be processed by this process are used fishing nets, plastic bags, food packaging, plastic bottle, like PET bottles, plastic films and sheets, carpets such as Nylon-based carpets, product packaging material like polystyrene, fabrics, like Nylon, polyester, PET fabrics, shoes, tires. The powdered polymer feed may be obtained by any means. Harder polymer products may be 5 grinded to obtain a suitable powder. Preferably the powdered polymer waste is obtained in a cryogenic milling process of waste polymer products. Applicants found that by cryogenic milling polymer particles may be obtained by simple means. it is found that the cryogenic milling may be effectively performed on polymer products of different sizes and/or composition. By decreasing the temperature the polymer becomes brittle and is easily milled to smaller particles. A further advantage is that the process can use polymer products which are contaminated. A further advantage is that a more stable feedstock for the combustion or partial combustion may be obtained in terms of its composition when starting from an in time varying mixture of different polymer waste. The powdered polymer feed can be easily homogenised thereby averaging its composition. This allows the use of waste plastic feedstock having widely varying composition in combination with a stable combustion process. The process can further use polymers which are not suited for recycle to its virgin state because of loss of technical properties due to past recycling/reuse cycles. The process can also convert mixtures of polymers which cannot be separated into discrete fractions. Further the process can convert polymer films which are otherwise difficult to recycle.
    Larger waste polymer products may be pre-treated to reduce their size prior to cryogenic milling by means of conventional techniques such as cutting, tearing and/or crushing. Preferably any inorganic contaminants, like sand or soil, is removed from the waste polymer products prior to performing a cryogenic milling step. Such a removal step may be performed by water washing of the waste polymer product. If such removal is difficult, like when processing used carpets, it may also be possible to remove these inorganic contaminants after performing the cryogenic step. For example by making use of the difference in mass density of the polymer material and the inorganic contaminants. Such separation may be performed by for example cyclone separation. The waste polymer products do not necessarily be dry. Some water, for example sea water, may be present wherein care is taken that the powdered polymer feed does not contain high amounts of potassium. In the cryogenic milling the water will solidify and subsequently by sublimation be removed from the solid polymer particles. Sublimation will be favoured by using dry gasses. The cryogenic milling may be performed by using cryogenic milling technology as for example described in US4406411, US4483488, US3885744 and US5203511. The milling itself may be performed in a grinding mill in the presence of a coolant. The coolant is preferably a liquid gas, more preferably a inert liquid gas. The liquid gas may be a liquid permanent gas such as helium, hydrogen, neon, nitrogen, oxygen, and normal air. Preferably liquid air and more preferably liquid nitrogen is used as a coolant. The temperature at which the milling takes place is suitably at the boiling temperature of the liquid gas and slightly above said temperature. The temperature in step (a) is suitably below minus 150 °C (- 150 °C) and preferably below minus 180 (-180 °C). The cryogenic milling may be performed using liquid nitrogen using the cooling and grinding technology called PolarFit® Cryogenic Reduction Solutions as offered by Air Products. In such a process the liquid nitrogen may be added directly to the mill chamber of the grinding mill. The liquid gas may also be provided to a conveyor, like a screw conveyor, where the waste polymer product is cooled to its desired low temperature before it enters the mill chamber as for example described in US3771729. For larger shaped waste polymer products it may be desirable to contact the waste products in a so-called tunnel freezer as for example described in US4175396.
    Liquid nitrogen is the preferred liquid gas used in the cryogenic milling because it is easily made in large quantities in the above described air separation process. The advantage is that now both the liquid nitrogen and the oxygen as prepared in such an air separation step is advantageously used in the method and process according to this invention. The liquid nitrogen will evaporate thereby effectively cooling the waste polymer product to well below their glass transition temperatures. The polymers become brittle and are easily grinded to a powder. Alternatively liquid air may be used which is formed in such an air separation unit and which may be separated as a separate product. The oxygen produced in such a process may then be obtained as the above referred to oxygen enriched gas. If nitrogen is used in the cryogenic milling any evaporated and used nitrogen may subsequently be used as a carrier gas to transport the polymer particles to the burners of the boiler. Another part of the gaseous nitrogen may be returned to the air separation process to be liquified and reused in the cryogenic milling.
    The size of the powdered polymer particles is suitably small such that a full combustion of the polymers to mainly water and carbon dioxide takes place. The size will be comparable to the size of the coal powder used in the state of the art process. Preferably the size is such that more than 90 wt% of the particles pass a 16 mesh sieve. and even more preferable pass a 100 mesh sieve. The average particle size is preferably between 30 and 100 micron.
    The cryogenic milling may be performed in the vicinity of where the combustion takes place. This is advantageous because then it is possible to also have an air separation process at the same location to provide for the liquid nitrogen for the cryogenic milling and for the oxygen enriched gas for the combustion. The cryogenic milling may also be performed closer to the source of the waste polymer product. For example a municipal waste plant may be equipped with a cryogenic milling facility. The preferred liquid nitrogen may be supplied to this municipal waste plant by means of a pipeline or by road or train from an air separation plant. Alternatively a mobile cryogenic milling unit, for example on a truck, may be used. Such a mobile unit may be preferred when temporarily more polymer waste is produced at one location. The polymer particles, optionally pelletised, may then be transported to the power plant. This power plant may be at the same facility as the air separation process. This facility to perform the power generation may source its powdered polymer particles from more than one cryogenic milling processes as described above.
    The combustion of the powdered polymer feed or of the powdered polymer particles makes use of an oxygen gas enriched in oxygen as obtained in the air separation process. Such an oxygen enriched gas having may have an oxygen content of more than 80 vol.%, suitably has an oxygen content of more than 90 vol.%, preferably more than 95 vol.% and even more preferably more than 99 vol.%. Such an oxygen enriched gas is preferably diluted with a carbon dioxide comprising recycle gasresulting in an oxygen content in the oxygen containing gas of suitably between 0.2 and 0.4 vol.% and a nitrogen content of below 0.2 vol% and wherein the oxygen containing gas further comprises carbon dioxide. This oxygen comprising gas is contacted with the powdered polymer feed or particles in the boiler. The oxygen containing gas is preferably prepared in the air separation process described above. Such a process may be used to adapt a coal fired power plant, wherein the coal is replaced by the polymer particles as feed and the air by the oxygen containing gas. By adding an air separation unit and a cryogenic milling process a carbon dioxide generating coal fired power plant can be adapted to a process which makes use of a waste polymer feed and generated a highly concentrated carbon dioxide flue gas which can be more easily stored in underground reservoirs. The fired boiler may have to be adapted. By making use of carbon dioxide as a carrier gas for the polymer particles in the feed to the burners of the coal fired power plant and/or by adding carbon dioxide when combusting one has means to control the temperature without diluting the flue gas in carbon dioxide. Preferably polymer particles are used having a low level of contaminants or no contaminants. This will result in that no ash is formed which simplifies the process.
    The oxygen content in the oxygen containing gas including the recycle gas is preferably such that the adiabatic flame temperature is between 1600 and 2200 C and the flue gas temperature in the boiler is between 900 and 1200 C.
    Preferably the air separation process produces liquid nitrogen for use in the cryogenic milling and gaseous and/or liquid oxygen for use in the combustion . The oxygen may be prepared as liquid oxygen to simplify storage and/or may be obtained as gaseous oxygen for direct use in the combustion.
    The invention shall be illustrated using the following Figure 1. In Figure 1 a process according to the invention is shown. In a coal power plant a boiler (8) and a steam turbine (10) will be present. By adding an air separation process (5), a cryogenic milling (2} and a flue gas dryer (12) and a carbon dioxide condenser (14) a process is obtained having the above described advantages. in such a process a waste polymer product (1) is reduced in size in a cryogenic milling unit (2) to obtain powdered polymer particles (6) by contacting the waste polymer product with liquid nitrogen (4). The polymer particles (6) are fully combusted in the presence of substantially pure oxygen in boiler (8) to obtain a flue gas (9) of substantially only water and carbon dioxide. In boiler (8) high pressure steam (11) is generated which is expanded in steam turbine (10) to generate electricity. The water in the flue gas (9) is condensed in water separated (12) and separated as liquid water {13). The dried flue gas (14) is partly recycled as recycle (15) to the boiler {8) where it is used to dilute the oxygen enriched gas (7) as obtained in the air separator (5). The carbon dioxide in the dried flue gas is condensed in condenser (16) and the liquid carbon dioxide (17) can be stored in sub surface reservoirs or used in for example greenhouses. The liquid nitrogen (4) and the oxygen enriched gas (7) are obtained in air separation unit (5) using air (3} as feed. The liquid nitrogen (4) is used in the cryogenic milling (2).
    In the above process scheme the air separation unit may be a cryogenic air distillation process comprising an air compressor which air. This compressor may be driven directly or indirectly by steam as obtained in steam turbine (10) or by the electricity obtained by means of steam turbine (10).
    In the water separator {12) water suitably condenses in an indirect heat exchange step using a colder fluid as the cooling medium. This colder fluid may be obtained in the air separation process (5) or in the cryogenic milling process (2). Exemplary colder fluids may be oxygen enriched gas, liquid air, liquid nitrogen, evaporated nitrogen as obtained in the cryogenic milling (2).
    Alternatively part of flue gas (9) may be recycled to dilute the oxygen enriched gas (7} to obtain the oxygen comprising gas of step (a) of the process according to this invention.
    Preferably the carbon dioxide as present in the dried flue gas is condensed in a condenser or an indirect heat exchange step using a colder fluid as the cooling medium. This colder fluid may be obtained in the air separation process {5) or in the cryogenic milling process (2). Exemplary colder fluids may be oxygen enriched gas, liquid air, liquid nitrogen, evaporated nitrogen as obtained in the cryogenic milling (2).
    权利要求:
    Claims (28)
    [1]
    A method of modifying a coal-fired power plant comprising a powdered coal supply, an air supply, burners, boilers and a steam expansion generator, and a flue gas stream, wherein the coal supply is replaced with a powdered polymer supply, and the air supply is replaced by an oxygen supply, connected to an upstream air separation process, resulting in a flue gas stream rich in carbon dioxide and water.
    [2]
    The method of claim 1, wherein the feed of powdered polymer is powdered polymer waste.
    [3]
    A method according to claim 2, wherein the powdered polymer waste is obtained in a cryogenic grinding process of polymer waste products.
    [4]
    The method of claim 3, wherein the cryogenic grinding process uses liquid nitrogen obtained in the air separation process.
    [5]
    A method according to any one of claims 1 to 4, wherein the air separation process is thermally integrated with a liquefied natural gas (LNG) regasification plant.
    [6]
    A method according to any one of claims 1 to 5, wherein the flue gas stream is connected to a water separator,
    [7]
    A method according to claim 5, wherein the water separator comprises an indirect heat exchanger in which the temperature of the flue gas is reduced by using a heat exchange with a colder fluid in such a way that water condenses, and wherein the colder fluid has a fluid obtained in the air separation process or in the optional cryogenic grinding process.
    [8]
    A method according to any one of claims 6 to 7, wherein a carbon dioxide condenser is positioned downstream of the water separator.
    [9]
    The method of claim 8, wherein the output of the carbon dioxide condenser for liquid carbon dioxide is connected to means for transporting the liquid carbon dioxide to a subterranean reservoir.
    [10]
    A method according to any one of claims 1 to 9, to which flue gas recycling has been added.
    [11]
    A method of generating electricity comprising the steps of: (a) combustion of powdered polymer particles, using a gas comprising oxygen, in a boiler to generate steam and a flue gas, and (b} expanding steam in a steam expansion generator to generate electricity.
    [12]
    A method according to claim 11, wherein in step {a) the powdered polymer particles are combusted into a flue gas consisting of carbon dioxide and water by contacting the polymer particles with a gas comprising oxygen, whereby the oxygen content in the gas comprising oxygen is between 0.2% by volume and 0.4% by volume, and the nitrogen content is less than 0.2% by volume, and wherein the gas comprising oxygen additionally comprises carbon dioxide and water,
    [13]
    A method according to any one of claims 11 to 12, wherein the feed of powdered polymer is powdered polymer waste.
    [14]
    The method of claim 13, wherein the powdered polymer waste is obtained in a cryogenic grinding process of polymer waste products.
    [15]
    The method of claim 14, wherein the cryogenic grinding process uses liquid nitrogen as obtained in an air separation process, and wherein the oxygen of a gas comprising oxygen is obtained in the same air separation process.
    [16]
    The method of claim 15, wherein the air separation process is a cryogenic air distillation process.
    [17]
    The method of claim 13, wherein the cryogenic air distillation process comprises an air compressor, said air compressor being driven directly or indirectly by steam as obtained in step (a), or driven by the electricity obtained in step (a). b).
    [18]
    A process according to any one of claims 15 to 17, wherein the cryogenic air distillation process is thermally integrated with a liquefied natural gas (LNG) regasification plant.
    [19]
    A method according to any one of claims 1 to 18, wherein the flue gas comprises water, and wherein the water is separated by condensing the water in a water separator, and wherein the condensed water is separated from the residual gaseous flue gas, resulting in a dried flue gas is obtained.
    [20]
    The method of claim 19, wherein the water condenses in an indirect heat exchange step using a colder fluid as the cooling medium, and wherein the colder fluid is obtained in an air separation process or in a cryogenic grinding process.
    [21]
    A method according to any one of claims 19 to 20, wherein a portion of the flue gas obtained upstream or downstream of the water separator is recycled to step (a) in such a way as to dilute a more concentrated oxygen gas, to obtain the gas comprising oxygen from step (a).
    [22]
    A method according to any one of claims 19 to 21, wherein the carbon dioxide as contained in the dried flue gas is condensed.
    [23]
    The method of claim 22, wherein the carbon dioxide condenser condenses in an indirect heat exchange step using a colder fluid as the cooling medium, and wherein the colder fluid is obtained in an air separation process or in a cryogenic grinding process.
    [24]
    A method according to any one of claims 22 to 23, wherein the condensed carbon dioxide is stored in a subterranean reservoir.
    [25]
    A method according to any one of claims 13 to 24, wherein the powdered polymer waste is a mixture of different polymer waste products.
    [26]
    The method of claim 25, wherein the mixture of different polymer waste products comprises at least two polymers from the list of polymers consisting of LDPE (Low Density Polyethylene), HDPE (High Density Polyethylene); PP (polypropylene); PS (polystyrene); PVC (polyvinyl chloride); PET (polyethylene terephthalate); PUT (polyurethanes) and PP&A fibers (polyphthalamide fibres).
    [27]
    The method of claim 26, wherein the blend comprises polystyrene.
    [28]
    A method according to any one of claims 14 to 21, wherein the temperature in the cryogenic grinding process is less than -150°C, and preferably is less than -180°C.
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    NL2023807|2019-09-11|
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