CN116531902A - System for coupling carbon capture and hydrocarbon production and method for comprehensively utilizing carbon dioxide - Google Patents

System for coupling carbon capture and hydrocarbon production and method for comprehensively utilizing carbon dioxide Download PDF

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Publication number
CN116531902A
CN116531902A CN202310628443.4A CN202310628443A CN116531902A CN 116531902 A CN116531902 A CN 116531902A CN 202310628443 A CN202310628443 A CN 202310628443A CN 116531902 A CN116531902 A CN 116531902A
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carbon dioxide
carbon
catalytic reaction
gas
stage
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Inventor
罗海中
范永春
曾少雁
孙张伟
林海周
王晓东
李伟科
吴大卫
薛榕
岳海荣
马奎
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China Energy Engineering Group Guangdong Electric Power Design Institute Co Ltd
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China Energy Engineering Group Guangdong Electric Power Design Institute Co Ltd
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Priority to CN202310628443.4A priority Critical patent/CN116531902A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention discloses a system for coupling carbon capture and hydrocarbon production and a method for comprehensively utilizing carbon dioxide. The system for coupling carbon trapping and hydrocarbon production comprises a carbon trapping system, a catalytic reaction system and an oil separation system, and has the advantages of being integrated, suitable for large-scale treatment of industrial flue gas, low in energy consumption, environment-friendly and the like. Meanwhile, the comprehensive utilization method of carbon dioxide provided by the invention comprises two-stage pressure swing adsorption, catalytic reaction and multi-stage condensation, so that the method not only can effectively concentrate the carbon dioxide in the flue gas step by step, but also can convert the carbon dioxide into hydrocarbon product gas with more carbon atoms and higher product value without electrolysis, and can effectively separate oily hydrocarbon products.

Description

System for coupling carbon capture and hydrocarbon production and method for comprehensively utilizing carbon dioxide
Technical Field
The invention relates to the technical field of carbon dioxide recovery and utilization, in particular to a system for coupling carbon capture and hydrocarbon production and a method for comprehensively utilizing carbon dioxide.
Background
The emission of greenhouse gases causes global warming, affects human survival and social development, and is critical to reduce carbon dioxide emissions and develop carbon dioxide resource regeneration technologies in order to cope with global climate change.
Carbon dioxide capture, utilization and sequestration technology (CCUS) can capture carbon dioxide discharged in industrial utilization and other processes, and carry out resource utilization on the carbon dioxide, so that the carbon dioxide is one of key technologies for realizing large-scale carbon emission reduction worldwide in the future, and is one of important technical choices for realizing long-term emission reduction and deep low-carbon transformation of an energy system. However, the existing carbon dioxide capturing device and the conversion device are generally independent from each other, and cannot directly perform chemical conversion on carbon dioxide after capturing. If the carbon dioxide capturing and chemical conversion processes can be combined, the cost required by the carbon dioxide storage and transportation processes can be avoided, the capturing and conversion integration of the carbon dioxide is realized, the problem of low direct carbon dioxide utilization rate of the traditional CCUS technology is solved, and the overall cost of the CCUS technology is reduced.
In this regard, expert scholars at home and abroad propose some integrated schemes for capturing and converting carbon dioxide. For example, patent CN 111690946a proposes a device for coupling intermittent carbon dioxide capture and conversion, capturing carbon dioxide by an absorption method, and further converting carbon dioxide into methanol by photoelectrocatalysis; patent CN 114522525A proposes an integrated system comprising a carbon dioxide capture module, an electrochemical reaction module and a bio-fermentation reaction module; patent CN 108117045A proposes a solution for co-production of synthesis gas by coupling carbon dioxide capture with a methane reforming process. Although the technical schemes can reduce the overall cost of the CCUS technology to a certain extent and realize the integration of carbon dioxide capture and utilization, the schemes mainly adopt traditional electro-catalysis in the catalysis process, have complex process and higher energy consumption, and are not beneficial to large-scale production.
Meanwhile, the conversion rate of carbon dioxide is low, the conversion products are mainly C1 products, and the technical scheme for converting the carbon dioxide into long-chain hydrocarbon with higher energy and higher value is lacking.
Accordingly, there is a need to develop an integrated, low energy-consuming, full-flow system and method for producing long-chain hydrocarbons that simultaneously achieves efficient carbon capture and catalytic conversion of carbon dioxide.
Disclosure of Invention
Aiming at the problems of higher cost, low integration degree and lack of carbon dioxide low-cost long-chain hydrocarbon preparation technology of the current CCUS technology, the invention provides a full-flow process for producing long-chain hydrocarbon by carbon capture and catalytic conversion. Carbon dioxide in the flue gas is captured mainly through a Pressure Swing Adsorption (PSA) system, and is conveyed into a catalytic reaction device to generate saturated alkane with carbon atoms more than or equal to 5, and the generated oil is further recovered through a condensation system, so that low-cost carbon dioxide capturing and conversion integration is realized.
In order to overcome the problems, the invention aims to provide a system for coupling carbon capture and hydrocarbon production and a method for comprehensively utilizing carbon dioxide.
Specifically, the purpose and the conception of the invention are as follows: the invention provides a method for comprehensively utilizing carbon dioxide, which effectively couples carbon capture and hydrocarbon production; the method comprises the following steps:
firstly, the carbon dioxide in the flue gas is concentrated step by adopting a two-stage PSA technology. The whole device has no steam consumption, no waste residue, no waste liquid and no toxic and harmful gas emission, and plays a role in energy conservation and environmental protection. And secondly, the catalytic system synthesizes clean gasoline based on catalysis, waste heat is the only energy source, electrolysis is not needed, carbon dioxide and non-drinking water in industrial waste gas are synthesized into pure renewable clean gasoline without pollutants and heavy metals in one-step catalytic reaction, the technical cost is low, the pollution is small, the modularization is easy, and the added value of the product is high. Finally, the process flow realizes the integration of carbon capturing, converting and product separating systems, reduces the overall cost of the CCUS technology, and provides a new mode for carbon capturing and utilizing technologies.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a system for coupling carbon capture to hydrocarbon production, comprising a carbon capture system, a catalytic reaction system, and an oil separation system;
the carbon capture system comprises an induced draft fan, a cooler, a first booster fan, a first vacuum pump, a second booster fan, a second vacuum pump, a first pressure swing adsorption device, a second pressure swing adsorption device and CO 2 A compressor;
the catalytic reaction system comprises a catalytic reactor;
the oil separation system comprises a plurality of condensers which are used for realizing multistage condensation;
an induced draft fan in the carbon capture system is sequentially connected with a cooler, a first booster fan, first pressure swing adsorption equipment, a first vacuum pump, a second booster fan, second pressure swing adsorption equipment, a second vacuum pump and CO through pipelines 2 The compressor is connected and used for capturing carbon dioxide;
CO in the carbon capture system 2 The compressor is connected with the catalytic reactor through a pipeline and is used for utilizing heat energy to convert CO 2 Catalytic conversion to saturated hydrocarbons;
the catalytic reactor is connected with the condenser through a pipeline and is used for separating and purifying hydrocarbon.
In some embodiments, the first pressure swing adsorption apparatus in the carbon capture system comprises a number of adsorption towers, a buffer tank, a flow controller, and a vacuum pump;
the adsorption towers are connected in series through pipelines, and a flow controller is arranged between every 2 adsorption towers and used for realizing uniform lifting and uniform lowering.
In some embodiments, the second pressure swing adsorption apparatus in the carbon capture system comprises a number of adsorption towers, a buffer tank, a flow controller, and a vacuum pump;
the adsorption towers are connected in series through pipelines, and a flow controller is arranged between every 2 adsorption towers and used for realizing uniform lifting and uniform lowering.
In one embodiment, a surge tank in the carbon capture system is used for pressure stabilization of a fluid (e.g., gas or liquid).
Specifically, since the pressure of a fluid (e.g., gas or liquid) is greatly changed after the fluid is depressurized (evacuated) or pressurized into a pipeline, the flow rate control is liable to be uneven, and thus it is necessary to provide a buffer tank to improve the continuity of the output gas flow and the stability of the pressure.
In some embodiments, the adsorption tower is connected to at least 1 vacuum pump, 1 booster fan.
In some embodiments, the adsorption tower top is provided with an evacuation pipeline for evacuating the gas with the volume fraction of less than or equal to 5%.
In some embodiments, the carbon capture system further comprises a steam-water separator disposed between the first booster fan and the first pressure swing adsorption apparatus via a conduit for separating gas and removing water.
In some embodiments, the catalytic reaction system comprises 2-5 catalytic reactors, the catalytic reactors are in parallel connection, and each catalytic reactor is respectively connected with the CO 2 The compressor and the condenser are connected.
In some embodiments, the catalytic reactor is provided with a heat source steam interface and a heat exchange assembly for providing a heat source to the reactor.
In some embodiments, the catalytic reactor is provided with an inlet for carbon dioxide and desalination feedstock, a product gas outlet.
In some embodiments, the catalytic reactor further comprises a temperature sensing controller, a pressure sensing controller.
In some embodiments, the oil separation system includes 3-5 condensers for achieving multi-stage condensation.
In some preferred embodiments, the oil separation system includes a first condenser, a second condenser, and a third condenser. And the first condenser, the second condenser and the third condenser are in a serial connection relationship and are used for realizing three-stage condensation.
In some embodiments, the oil separation system further comprises at least 2 fluid reservoirs; and the liquid storage tank is arranged below the condenser and is used for recycling hydrocarbon and wastewater by utilizing gravity, so that the low-energy consumption oil-gas separation is facilitated.
In a second aspect, the invention provides a method for comprehensive utilization of carbon dioxide, comprising the following steps:
1) The industrial flue gas containing 3 to 20 percent (volume fraction) of carbon dioxide enters a carbon trapping system after passing through a draught fan, and compressed carbon dioxide product gas is obtained through cooling, two-stage pressure swing adsorption and gas compression;
2) The compressed carbon dioxide product gas enters a catalytic reaction system, is mixed with a hydrogen source, and is subjected to catalytic reaction to obtain saturated alkane-containing product gas;
3) Collecting and conveying the product gas containing saturated alkane to an oil separation system, and obtaining hydrocarbon products through multistage continuous condensation treatment;
wherein, the carbon dioxide content of the compressed carbon dioxide product gas in the step 1) is more than or equal to 80 percent in terms of volume fraction.
In some embodiments, the method for comprehensive utilization of carbon dioxide comprises the steps of:
1) After passing through an induced draft fan, industrial flue gas containing 5-15% (volume fraction) of carbon dioxide enters a carbon trapping system, and compressed carbon dioxide product gas is obtained through cooling, first pressurization, first pressure swing adsorption, first pressure reduction, second pressurization, second pressure swing adsorption, second pressure reduction and gas compression;
2) The compressed carbon dioxide product gas enters a catalytic reaction system, is mixed with a hydrogen source, and is subjected to catalytic reaction to obtain saturated alkane-containing product gas;
3) Collecting and conveying the product gas containing saturated alkane to an oil separation system, and obtaining hydrocarbon products through multistage continuous condensation treatment;
wherein, the carbon dioxide content of the compressed carbon dioxide product gas in the step 1) is more than or equal to 82 percent in terms of volume fraction.
In some embodiments, step 1) further comprises a water removal process for removing water generated during cooling, pressurization and depressurization, thereby facilitating carbon dioxide enrichment.
In some embodiments, the adsorbent used in step 1) for the primary pressure swing adsorption and the secondary pressure swing adsorption is selected from at least one of activated carbon, molecular sieves. Specifically, the molecular sieve is one or more of an aluminum silicate molecular sieve and an all-silicon molecular sieve.
In some embodiments, the second pressurizing of step 1) is specifically performed by controlling the gas pressure to be 0.15MPa to 0.50MPa.
In some embodiments, the second pressurizing of step 1) is specifically performed by controlling the gas pressure to be 0.18MPa to 0.20MPa.
In some embodiments, the hydrogen source in the catalytic reaction of step 2) is one or more of water, hydrogen gas.
In some embodiments, the water is from industrial water in a tap water pipe or condensed water from steam in a system coupled with hydrocarbon production.
In some embodiments, the catalyst used in the catalytic reaction of step 2) is a metal nanocatalyst.
Specifically, the catalyst is a metal nanoparticle type catalyst, and the metal is selected from at least one of Fe, co, ni, mn, cu.
In some embodiments, the amount of catalyst packing in the catalytic reaction system of step 2) is flexibly adjustable according to project scale.
In some embodiments, step 2) the catalytic reaction is heated with hot steam.
Specifically, the source of the hot steam is an auxiliary steam header of a certain power plant, and the temperature of the hot steam is 140-160 ℃.
In some embodiments, the temperature of the catalytic reaction of step 2) is 140 to 160 ℃.
In some preferred embodiments, the temperature of the catalytic reaction of step 2) is 145 to 165 ℃.
In some embodiments, the gauge pressure of the catalytic reaction of step 2) is from 0.5 to 0.8MPa.
In some embodiments, the carbon dioxide single pass carbon conversion of the catalytic reaction of step 2) is between 10% and 25%.
In some embodiments, step 2) the saturated alkane-containing product gas comprises C 1 ～C 4 Saturated alkanes and C 5 ～C 11 The mass ratio of the saturated alkane is (1-1.3): 1.
In some preferred embodiments, the saturated alkane-containing product gas of step 2) comprises C in mass fraction 1 ～C 4 Saturated alkanes of (2): 5% -10%; c (C) 5 ～C 11 Saturated alkanes of (2): 5 to 10 percent.
In some more preferred embodiments, the saturated alkane-containing product gas composition of step 2) in mass fraction is as follows: CH (CH) 4 ：2.05％，C 2 H 6 ：3.85％，C 3 H 8 ：0.59％，C 4 H 10 ：0.39％，C 5 H 12 ：0.56％，C 6 H 14 ：0.86％，C 7 H 16 ：0.99％，C 8 H 18 ：0.86％，C 9 H 20 ：0.85％，C 10 H 22 ：0.68％，C 11 H 24 ：0.51％。
In some embodiments, step 3) the multistage continuous condensation process is a three-stage condensation, the specific operation of which is:
the refrigeration temperature of the primary condensation is controlled to be 2-12 ℃, and the primary condensation is used for mainly treating water and oil gas heavy components, intercepting most of water and reducing the possibility of frosting of the water or oil gas heavy components in the subsequent two-stage refrigeration;
controlling the refrigerating temperature of the secondary condensation to be-20 ℃ to-40 ℃ and liquefying and recovering part of oil gas;
the refrigeration temperature of the three-stage condensation is controlled to be-55 ℃ to-75 ℃ and is used for further recovering oil gas.
In some preferred embodiments, the multistage continuous condensation process of step 3) is a three-stage condensation, the specific operation of which is:
the refrigeration temperature of the primary condensation is controlled to be 3-7 ℃, and the primary condensation is used for mainly treating water and oil gas heavy components, intercepting most of water and reducing the possibility of frosting of the water or oil gas heavy components in the subsequent two-stage refrigeration;
controlling the refrigerating temperature of the secondary condensation to be-25 ℃ to-30 ℃ and liquefying and recovering part of oil gas;
the refrigeration temperature of the three-stage condensation is controlled to be-60 to-70 ℃ and is used for further recovering oil gas.
In some embodiments, step 3) further comprises utilizing gravity to recover wastewater and hydrocarbon products in the multistage continuous condensation process.
The beneficial effects of the invention are as follows: the comprehensive utilization method of carbon dioxide provided by the invention comprises two-stage pressure swing adsorption, catalytic reaction and multi-stage condensation, and not only can effectively concentrate the carbon dioxide in the flue gas step by step, but also can convert the carbon dioxide into hydrocarbon product gas with more carbon atoms and higher product value without electrolysis, and can effectively separate oily hydrocarbon products. The system for coupling carbon trapping and hydrocarbon production, which is matched with the system, comprises a carbon trapping system, a catalytic reaction system and an oil separation system, and has the advantages of integration, suitability for large-scale treatment of industrial flue gas, low energy consumption, environmental protection and the like. The method comprises the following steps:
(1) The invention uses two-stage PSA technique to concentrate the carbon dioxide in the flue gas step by step, and the trapping system of the invention has no steam consumption, no waste residue, waste liquid and no toxic and harmful gas emission, thus playing the roles of energy saving, environmental protection and energy saving.
(2) The invention synthesizes clean gasoline by adopting a catalytic technology, can be directly converted into a product with high added value in one step, and the conversion rate of carbon dioxide can reach 10-25%.
(3) The invention integrates the carbon capturing, converting and product separating system, realizes the integration of carbon capturing, converting and storing, and reduces the whole technical cost.
Drawings
FIG. 1 is a schematic diagram of a system for coupling carbon capture with hydrocarbon production in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "connected," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; may be directly connected, indirectly connected through an intermediate medium, or may be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
The starting materials, reagents or apparatus used in the examples are all commercially available from conventional sources or may be obtained by methods known in the art unless otherwise specified. Unless otherwise indicated, assays or testing methods are routine in the art.
Referring to FIG. 1, a system for coupling carbon capture with hydrocarbon production in accordance with an embodiment of the present invention is described.
The decarbonizing flue gas treatment system comprises a carbon trapping system, a catalytic reaction system and an oil separation system, wherein the carbon trapping system is connected with the catalytic reaction system and the oil separation system in sequence through pipelines;
the carbon capture system includes: induced draft fan, cooler, booster fan, pressure swing adsorption equipment PSA1, vacuum pump 1, booster fan, pressure swing adsorption equipment PSA2, vacuum pump 2 and CO 2 A compressor;
the catalytic reaction system comprises: reactor 1, reactor 2 and reactor 3;
the oil separation system includes: the device comprises a first-stage condenser, a second-stage condenser, a third-stage condenser, a heavy hydrocarbon tank and a wastewater tank;
an induced draft fan in the carbon trapping system is connected with a cooler, a booster fan 1, a pressure swing adsorption device PSA1, a vacuum pump 1, a booster fan 2, a pressure swing adsorption device PSA2, a vacuum pump 2 and CO in series 2 The compressor is connected for collecting the flue gas and realizing CO 2 Is trapped;
CO in a carbon capture system 2 The compressors are respectively connected with a reactor 1, a reactor 2 and a reactor 3 in the catalytic reaction system, the reactor 1, the reactor 2 and the reactor 3 are in parallel connection, and the 3 reactors are catalytic reactors for realizing batch treatment and catalytic conversion of carbon dioxide into hydrocarbon (products); meanwhile, the reactor 1, the reactor 2 and the reactor 3 are provided with feed ports of a hydrogen source for supplying a hydrogen source (e.g., water);
the product outlets of the reactor 1, the reactor 2 and the reactor 3 in the catalytic reaction system are connected with a first-stage condenser in the oil separation system through pipelines and then are sequentially connected with a second-stage condenser and a third-stage condenser;
the first-stage condenser and the second-stage condenser are respectively connected with a wastewater tank and are used for recycling wastewater generated in the condensation process;
the three-stage condenser is provided with a heavy hydrocarbon product outlet, and the outlet is connected with a heavy hydrocarbon tank for obtaining separated hydrocarbon.
In an embodiment of the first aspect of the invention, a steam-water separator is provided between the booster fan 1 and the pressure swing adsorption apparatus PSA1 in the capturing system for removing free water.
In one embodiment, the pressure swing adsorption device PSA1 in the trapping system comprises 1 to 8 adsorption towers, a buffer tank, a flow controller and a vacuum pump, and is used for realizing uniform lifting and uniform lowering;
the adsorption towers are connected in series through pipelines, and a flow controller is arranged between every 2 adsorption towers;
each adsorption tower is connected with at least 1 vacuum pump, 1 booster fan and corresponding pipelines.
In one embodiment, the pressure swing adsorption apparatus PSA2 in the capture system comprises 1-8 adsorption columns, buffer tanks, flow controllers, and vacuum pumps; the adsorption towers are connected in series through pipelines, and a flow controller is arranged between every 2 adsorption towers and is used for realizing uniform lifting and uniform lowering;
each adsorption tower is connected with at least 1 vacuum pump, 1 booster fan and corresponding pipelines.
In one embodiment, a surge tank in the trapping system is used for pressure stabilization of a fluid (e.g., gas or liquid).
Specifically, since the pressure of a fluid (e.g., gas or liquid) is greatly changed after the fluid is depressurized (evacuated) or pressurized into a pipeline, the flow rate control is liable to be uneven, and thus it is necessary to provide a buffer tank to improve the continuity of the output gas flow and the stability of the pressure.
In one embodiment, in the trapping system, the top of each adsorption tower of the pressure swing adsorption device PSA1 and the pressure swing adsorption device PSA2 is connected with the air inlet of the other adsorption tower through a pipeline for realizing multiple adsorption cycles; and the adsorption tower top of the pressure swing adsorption equipment PSA2 is provided with an evacuation pipeline for evacuating the carbon dioxide gas with the content less than or equal to 5 percent.
In another embodiment, the booster fan 1 of the trapping system is coupled to the adsorption column of the first stage in the pressure swing adsorption apparatus PSA 1;
the adsorption tower of the last stage in the pressure swing adsorption equipment PSA1 of the trapping system is further connected with the vacuum pump, the vacuum pump 1 and the pressurizing fan 2 and then connected with the adsorption tower of the first stage in the pressure swing adsorption equipment PSA 2;
the "first stage" and "second stage" in the PSA of the capturing system are determined according to the contact time with the raw material gas, and the adsorption towers of different stages can realize multistage adsorption.
In one embodiment, the pressure swing adsorption apparatus PSA1 and pressure swing adsorption apparatus PSA2 in the capture system are identical in arrangement, wherein pressure swing adsorption apparatus PSA1 is used for carbon dioxide rough concentration (i.e., purification and concentration) and pressure swing adsorption apparatus PSA2 is used for carbon dioxide fine concentration (i.e., purification and concentration).
In one embodiment, reactor 1, reactor 2, and reactor 3 in the catalytic reaction system are catalytic reactors.
In one embodiment, the first stage condenser, the second stage condenser, and the third stage condenser in the oil separation system are substantially heat exchangers.
In one embodiment, the wastewater tank and the heavy hydrocarbon tank in the oil separation system are both liquid storage tanks.
A method for comprehensive utilization of carbon dioxide according to an embodiment of the present invention is described below with reference to fig. 1.
The comprehensive carbon dioxide utilizing process includes mainly carbon trapping, catalytic conversion and oil separating process, and includes the following steps:
(1) After passing through an induced draft fan, the industrial flue gas containing 5% -20% of carbon dioxide enters a carbon trapping system, and the carbon dioxide in the industrial flue gas can be purified to more than 80% (volume fraction) through cooling, pressurization, primary pressure swing adsorption, vacuumizing and depressurizing, pressurization, secondary pressure swing adsorption, vacuumizing and depressurizing, and compression, so that the compressed carbon dioxide is obtained;
(2) The compressed carbon dioxide enters a catalytic reaction system, is mixed with water (hydrogen source), and is converted into saturated alkane through catalytic reaction (the conversion rate of the carbon dioxide in the technical scheme is 10-25 percent);
(3) Collecting gaseous products, transporting the products through a pipeline, entering an oil separation system, condensing oil gas through three-stage condensation to obtain hydrocarbon, and storing the hydrocarbon in a heavy hydrocarbon tank;
wherein the adsorbent used in the first-stage pressure swing adsorption and the second-stage pressure swing adsorption in the step (1) is one or more of common aluminum silicate (not in the form of molecular sieves), activated carbon and molecular sieves;
the catalyst used in the step (2) is a metal nano catalyst.
In one embodiment, the source of the industrial flue gas is a coal-fired power plant at a temperature of 50-60 ℃ and comprises mainly N 2 、CO 2 And a small amount of SO 2 NOx, smoke, and the like.
In one embodiment, the carbon capture system is a two-stage pressure swing adsorption method for concentrating carbon dioxide in flue gas, namely a PSA1 stage (carbon dioxide rough concentration stage) and a PSA2 stage (carbon dioxide fine concentration stage);
the carbon trapping process in the method for comprehensively utilizing the carbon dioxide specifically comprises the following steps:
(1) Pretreatment: the carbon dioxide content in the industrial flue gas is about 12%, and the pretreated gas (the temperature is 40-50 ℃) is obtained through a draught fan, a cooler and a pressurizing fan 1;
(2) Primary pressure swing adsorption (i.e., PSA1 stage): the pretreated gas enters a steam-water separator to remove free water to obtain a raw material; then, the raw material gas enters a first adsorption tower in an adsorption state in the pressure swing adsorption equipment PAS1, easily-adsorbed components such as carbon dioxide, gaseous water and the like in the raw material gas are firstly absorbed, and components such as nitrogen, oxygen and the like which are not easily adsorbed are discharged from the tower top;
stopping ventilation when the adsorption front of the easily adsorbed component reaches the top of the tower soon, connecting the tower with other towers, carrying out uniform reduction for 3 times, and carrying out enrichment and concentration on carbon dioxide in the first adsorption tower preliminarily to obtain gas subjected to uniform reduction treatment;
pumping out the carbon dioxide in the first adsorption tower through vacuumizing, and sending the carbon dioxide into a buffer tank for stabilizing the pressure, wherein the concentration of the carbon dioxide reaches about 40% -45% (volume fraction);
after the vacuumizing is finished, carrying out 3 times of uniform lifting with other towers, and continuing to enter the next adsorption cycle until the carbon dioxide concentration at the bottom of the adsorption tower is 40% -45%;
the adsorption tower is depressurized to-0.06 to-0.07 MPa (gauge pressure) through a vacuum pump 1, and after gas is removed from the adsorbent, the gas is pressurized to 0.15 to 0.2MPa (gauge pressure) through a pressurizing fan 2, so that the product gas (the carbon dioxide content is about 44%) of a carbon dioxide crude concentration section is obtained;
(3) Two-stage pressure swing adsorption (i.e., PSA2 stage):
the product gas of the carbon dioxide crude concentration section is boosted to about 0.19MPa by a booster fan, enters an adsorption tower of the PSA2 section in an adsorption state, and is subjected to adsorption, 3 times of uniform pressure drop and vacuumizing;
if the carbon dioxide content of the gas at the bottom of the adsorption tower is less than 78% or the carbon dioxide content of the gas at the top of the adsorption tower is more than 5%, continuing the next adsorption cycle;
evacuating the mixed gas with the carbon dioxide content of less than or equal to 5% at the top outlet of the adsorption tower of the PSA2 section; obtaining a carbon dioxide product gas having a content of about 80% at the bottom of the adsorption column;
the adsorption tower is depressurized to-0.06 to-0.07 MPa (gauge pressure) by a vacuum pump 2, and the gas is separated from the adsorbent and passes through CO 2 Compressing by a compressor to obtain carbon dioxide product gas (volume fraction of carbon dioxide: about 85%);
wherein the adsorbent in the step (2) and the step (3) is one or more of common aluminum silicate (not in the form of molecular sieve), activated carbon and molecular sieve;
in the PSA1 section in the step (2), each adsorption tower sequentially undergoes adsorption, 3 times of pressure equalizing and reducing, vacuumizing, 3 times of pressure equalizing and increasing, final pressure increasing and other steps to enter the next adsorption cycle;
in the PSA2 section of the step (3), the adsorption tower is then subjected to 3 times of uniform rising and final rising of top tail gas with other towers, and then the adsorption tower enters the next adsorption circulation steps (2) and (3) again, and the whole operation process of primary pressure swing adsorption and secondary pressure swing adsorption is carried out at the temperature of gas entering the tower without additional heating or cooling. Moreover, the whole process is carried out at the temperature of the tower-entering raw material gas, so that no steam is consumed, no waste residue, waste liquid and no toxic and harmful gas are discharged;
taking a certain operation as an example, the process parameters of the two-stage pressure swing adsorption method are shown in table 1.
Table 1 process parameters of two stage pressure swing adsorption process
Note that: the contents in table 1 are all volume fractions;
sigma in Table 1 means "sum" or "total";
the carbon dioxide product gas in Table 1 is a carbon dioxide product gas obtained by a two-stage pressure swing adsorption process on a PSA2 stage adsorbent.
In one embodiment, the catalytic reaction system employs catalytic technology. The reaction system comprises 3 catalytic reactors connected in parallel, each catalytic reactor unit is provided with a heat source steam interface, a carbon dioxide and desalted water raw material inlet and a product gas outlet, and the reaction system is provided with complete temperature, pressure and flow sensing control devices.
In one embodiment, the catalytic reaction system further comprises a pressurizing device.
In one embodiment, the catalytic conversion in the method for comprehensively utilizing carbon dioxide is a catalytic process, and specifically comprises the following steps:
saturated hot steam (the temperature is about 150 ℃ and the gauge pressure is 0.4-0.5 Mpa) enters a heat exchange component of a catalytic reaction system from a heat supply pipeline through a distribution pipeline, and the system is gradually heated to the expected stable temperature (about 150 ℃); the heating temperature of the reactor is controlled by adjusting the flow of the steam pipeline;
the front end of the product carbon dioxide gas (the carbon dioxide content is more than or equal to 80 percent in terms of volume fraction) and desalted water which are prepared from the trapping system are taken as raw material gas and raw material water, and the raw material water and the raw material gas pipeline respectively enter a catalytic reactor after passing through a supercharging device, and the temperature of the reactor is controlled to be about 150 ℃, and the pressure is controlled to be 0.5-0.8 MPa (gauge pressure);
after entering a catalytic reactor, carbon dioxide and water are fully mixed in the reactor and are contacted with a metal nano catalyst to react, and partial carbon dioxide is converted into mixed hydrocarbon product gas (the carbon dioxide single-pass carbon conversion rate is 10% -25%), so as to obtain hydrocarbon-containing product (the hydrocarbon content is shown in table 2);
the feed gas for the catalytic reaction comprises 12% (mass percent) CO 2 And a small amount of H 2 O (water vapor); the catalytic reaction system obtains products with different content ratios of C1 to C12 and the like.
Specifically, taking a certain operation as an example, in the products with different content ratios of C1-C12 and the like, the content of the hydrocarbon of C1-C4 is 6.88 percent, and the content of the hydrocarbon of C5-C12 is 5.31 percent.
By analysis, taking a certain operation as an example, in products with different content ratios of C1 to C12 and the like, CH is calculated by mass fraction 4 ：2.05％，C 2 H 6 ：3.85％，C 3 H 8 ：0.59％，C 4 H 10 ：0.39％，C 5 H 12 ：0.56％，C 6 H 14 ：0.86％，C 7 H 16 ：0.99％，C 8 H 18 ：0.86％，C 9 H 20 ：0.85％，C 10 H 22 ：0.68％，C 11 H 24 ：0.51％。
The catalytic reaction system adopts a catalytic technology, adopts steam as heat supply energy by simulating the synthesis effect in the natural world and utilizing the effect of the metal nano catalyst, and synthesizes the renewable clean gasoline without pollutants and heavy metals in one-step catalytic reaction by using carbon dioxide and non-drinking water under the condition of no electrolysis process. The product generated by conversion and unreacted raw materials (namely hydrocarbon-containing product) are discharged in a gaseous form through a discharge hole of the reaction device and sent to a lower-stage oil separation system through a pipeline for product separation and extraction.
In one embodiment, the catalytic reaction system employs a catalyst that is a metal nanocatalyst; the metal nano catalyst is nano particles, the component is metal, and the metal is at least one selected from Fe, co, ni, mn, cu.
In one embodiment, the heavy hydrocarbon tank and in the oil separation system
The height that the wastewater tank set up is all less than the condenser for transport waste water and the hydrocarbon that condenses down with gravity realize energy-conserving effect.
In one embodiment, the oil separation system comprises a primary condenser, a secondary condenser, a tertiary condenser, an economizer, a separator, a heavy hydrocarbon tank, and a wastewater tank; the oil-gas separation system adopts a three-stage condensation process to separate oil from gas;
the three-stage condensation needs to control the temperature of the oil gas to be reduced to the dew point temperature corresponding to each component under the pressure of each component, different components of the oil gas are condensed into liquid state in a stage manner, and the low-concentration tail gas after full condensation is discharged through a chimney.
The three-stage condensation process specifically comprises the following steps:
the reactor obtained by the catalytic reaction system sequentially enters a first-stage condenser, a second-stage condenser and a third-stage condenser for three-stage condensation,
the first-stage condenser is arranged and controlled to obtain the refrigerating temperature of 3-7 ℃, and is mainly used for treating water and oil gas heavy components, intercepting most of water and reducing the possibility of frosting of the water or oil gas heavy components in the subsequent two-stage refrigeration;
setting and controlling a secondary condenser to obtain refrigeration temperature of minus 25 ℃ to minus 30 ℃ and liquefying and recycling part of oil gas; setting and controlling a three-stage condenser to obtain the refrigeration temperature of minus 60 to minus 70 ℃, and further recovering oil gas;
the liquid condensed by the refrigerator is conveyed into the heavy hydrocarbon tank under the action of gravity, and when the heavy hydrocarbon tank reaches a high liquid level, a pump is started to discharge the liquid; when the liquid level reaches a low level, the pump is turned off.
In some embodiments, the high level of the heavy hydrocarbon tank is set at 2/3 to 4/5 of its height and the high level of the heavy hydrocarbon tank is set at 1/5 to 1/3 of its height.
The system and the method for comprehensively utilizing the carbon dioxide have the greatest advantages that an upstream system and a downstream system are opened, centralized and unified regulation and control are realized, and the pressure swing adsorption system is regulated in real time according to the inlet pressure and flow requirements of the catalytic reaction device, so that the purposes of optimal system matching and lowest running cost are realized.
The above embodiments are merely preferred embodiments of the present invention, and are not intended to limit the present invention, but any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A system for coupling carbon capture with hydrocarbon production, comprising a carbon capture system, a catalytic reaction system, and an oil separation system;
the carbon capture system comprises an induced draft fan, a cooler, a first booster fan, a first vacuum pump, a second booster fan, a second vacuum pump, a first pressure swing adsorption device, a second pressure swing adsorption device and CO 2 A compressor;
the catalytic reaction system comprises a catalytic reactor;
the oil separation system comprises a plurality of condensers which are used for realizing multistage condensation;
an induced draft fan in the carbon capture system is sequentially connected with a cooler, a first booster fan, first pressure swing adsorption equipment, a first vacuum pump, a second booster fan, second pressure swing adsorption equipment, a second vacuum pump and CO through pipelines 2 The compressor is connected and used for capturing carbon dioxide;
CO in the carbon capture system 2 The compressor is connected with the catalytic reactor through a pipeline and is used for utilizing heat energy to convert CO 2 Catalytic conversion to saturated hydrocarbons;
the catalytic reactor is connected with the condenser through a pipeline and is used for separating and purifying hydrocarbon.
2. The system of carbon capture coupled with hydrocarbon production of claim 1, wherein the oil separation system comprises 3-5 condensers for achieving multi-stage condensation.
3. The carbon capture and hydrocarbon production coupling of claim 1 or 2The system is characterized in that: the catalytic reaction system comprises 2-5 catalytic reactors which are in parallel connection, and each catalytic reactor is respectively connected with the CO 2 The compressor and the condenser are connected.
4. The system of carbon capture coupled with hydrocarbon production of claim 2, wherein: the oil separation system further comprises at least 2 liquid storage tanks; and the liquid storage tank is arranged below the condenser and is used for recycling hydrocarbon and wastewater by utilizing gravity, so that the low-energy consumption oil-gas separation is facilitated.
5. The method for comprehensively utilizing the carbon dioxide is characterized by comprising the following steps of:
1) After passing through a draught fan, the industrial flue gas containing 3% -20% of carbon dioxide enters a carbon trapping system, and compressed carbon dioxide product gas is obtained through cooling, two-stage pressure swing adsorption and gas compression;
2) The compressed carbon dioxide product gas enters a catalytic reaction system, is mixed with a hydrogen source, and is subjected to catalytic reaction to obtain saturated alkane-containing product gas;
3) Collecting and conveying the product gas containing saturated alkane to an oil separation system, and obtaining hydrocarbon products through multistage continuous condensation treatment;
wherein, the carbon dioxide content of the compressed carbon dioxide product gas in the step 1) is more than or equal to 80 percent in terms of volume fraction.
6. The method for comprehensive utilization of carbon dioxide according to claim 5, wherein: the method comprises the following steps:
1) After passing through an induced draft fan, the industrial flue gas containing 5% -15% of carbon dioxide enters a carbon trapping system, and compressed carbon dioxide product gas is obtained through cooling, first pressurization, first-stage pressure swing adsorption, first depressurization, second pressurization, second-stage pressure swing adsorption, second depressurization and gas compression;
2) The compressed carbon dioxide product gas enters a catalytic reaction system, is mixed with a hydrogen source, and is subjected to catalytic reaction to obtain saturated alkane-containing product gas;
3) Collecting and conveying the product gas containing saturated alkane to an oil separation system, and obtaining hydrocarbon products through multistage continuous condensation treatment;
wherein, the carbon dioxide content of the compressed carbon dioxide product gas in the step 1) is more than or equal to 82 percent in terms of volume fraction.
7. The method for comprehensive utilization of carbon dioxide according to claim 5 or 6, wherein: the hydrogen source in the catalytic reaction in the step 2) is one or more of water and hydrogen.
8. The method for comprehensive utilization of carbon dioxide according to claim 6, wherein: the second pressurization in the step 1) is specifically to control the gas pressure to be 0.15-0.50 MPa in gauge pressure.
9. The method for comprehensive utilization of carbon dioxide according to claim 5 or 6, wherein: the catalyst used in the catalytic reaction in the step 2) is a metal nano catalyst; the temperature of the catalytic reaction in the step 2) is 140-160 ℃; the gauge pressure of the catalytic reaction in the step 2) is 0.5-0.8 MPa.
10. The method for comprehensive utilization of carbon dioxide according to claim 5 or 6, wherein: the multistage continuous condensation treatment in the step 3) is three-stage condensation, and the specific operation of the three-stage condensation is as follows:
controlling the refrigerating temperature of the primary condensation to be 2-12 ℃; controlling the refrigerating temperature of the secondary condensation to be-20 ℃ to-40 ℃; the refrigeration temperature of the three-stage condensation is controlled to be-55 ℃ to-75 ℃.
CN202310628443.4A 2023-05-30 2023-05-30 System for coupling carbon capture and hydrocarbon production and method for comprehensively utilizing carbon dioxide Pending CN116531902A (en)

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