CN114394883A - Method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electricity and green hydrogen to achieve near-zero carbon emission - Google Patents
Method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electricity and green hydrogen to achieve near-zero carbon emission Download PDFInfo
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- CN114394883A CN114394883A CN202111286319.1A CN202111286319A CN114394883A CN 114394883 A CN114394883 A CN 114394883A CN 202111286319 A CN202111286319 A CN 202111286319A CN 114394883 A CN114394883 A CN 114394883A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000003245 coal Substances 0.000 title claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002309 gasification Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000008878 coupling Effects 0.000 title claims description 12
- 238000010168 coupling process Methods 0.000 title claims description 12
- 238000005859 coupling reaction Methods 0.000 title claims description 12
- 230000005611 electricity Effects 0.000 title abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 49
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004146 energy storage Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 12
- 238000010248 power generation Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 6
- 238000005261 decarburization Methods 0.000 claims abstract description 5
- 239000002918 waste heat Substances 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000005338 heat storage Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of methanol preparation with zero carbon emission, and particularly discloses a method for preparing methanol with near zero carbon emission by using pulverized coal waste boiler gasification coupled with green electro-green hydrogen, which comprises the following steps: oxygen generated by the air separation device and oxygen generated by the water electrolysis device react with coal in the pulverized coal waste boiler gasification device together to obtain synthesis gas; the pulverized coal waste boiler gasification device recovers heat of high-temperature synthesis gas through a waste heat boiler and a steam superheater to produce high-pressure superheated steam, and the high-pressure superheated steam is sent to an air separation device to drive an air compressor turbine; the synthesis gas is sent to a heat recovery device for further heat recovery; sending the synthesis gas out of the heat recovery device to a purification device, removing only sulfur-containing acid gas without decarburization, and obtaining purified gas containing carbon monoxide, hydrogen and carbon dioxide; and one part of the electric energy generated by the new energy power generation system is sent to the water electrolysis hydrogen production device, one part of the electric energy is used by other electricity utilization facilities of the whole plant, and the other part of the electric energy is sent to the energy storage device for storage.
Description
Technical Field
The invention belongs to a method for preparing methanol with near-zero carbon emission and environmental protection, and particularly relates to a method for preparing methanol with near-zero carbon emission by gasifying pulverized coal waste boiler and coupling green electro-green hydrogen.
Background
The demand of methanol as one of important organic raw materials in the chemical industry is huge every year, the national methanol production capacity exceeds 8700 million tons/year as far as 2020, and the yield exceeds 6600 million tons. Due to the resource pattern of 'lean oil, rich coal and less gas' in China, the domestic production of methanol is mainly based on the route of preparing methanol from coal, and accounts for about 76% of the total production energy in China. The current widely used process for preparing methanol from coal comprises the following steps: and carrying out gasification reaction on oxygen generated by the air separation device and coal to generate crude synthesis gas, transforming the crude synthesis gas to adjust the content of carbon monoxide and hydrogen in the synthesis gas, purifying, desulfurizing and decarbonizing to obtain a methanol synthesis feed gas with a hydrogen-carbon ratio of 2.0-2.3, and then sending the methanol synthesis feed gas to a methanol synthesis device to produce a methanol product.
In the above process, in order to obtain a methanol synthesis raw material gas satisfying the requirement of hydrogen-carbon ratio, a part of carbon monoxide must be converted into hydrogen through a shift reaction, and as can be seen from the reaction formula, one mole of carbon dioxide is generated while one mole of hydrogen is generated, and both the carbon dioxide generated by the shift reaction and the carbon dioxide generated by the coal gasification reaction need to be removed in a purification unit and discharged into the atmosphere, so that a large amount of carbon elements are not utilized and are directly wasted, and a large amount of carbon is discharged. The utilization rate of carbon element in the raw material coal of the traditional coal-to-methanol route is estimated only to be about 40% preliminarily.
Meanwhile, a coal gasification device needs to be matched with an air separation device to provide required raw material oxygen for coal gasification reaction, and an air compressor of a core device of a large air separation device is mostly driven by steam, so that a coal-fired boiler needs to be matched with a traditional coal-to-methanol plant to supply high-pressure superheated steam, carbon elements in fuel coal are completely combusted and then discharged in a form of carbon dioxide, and the utilization rate of the carbon elements is zero.
Therefore, in summary, 60% of carbon element in the raw material coal and 100% of carbon element in the fuel coal in the traditional coal-to-methanol route are CO2The form is vented to the atmosphere.
The production industry with high carbon emission intensity of coal-based methanol can reduce the carbon emission in the production process by technical updating and upgrading, and the realization of carbon emission reduction or zero carbon emission production is the key for restricting the further development of the methanol industry.
Disclosure of Invention
Aiming at the problems existing in the prior art for preparing the methanol, the invention provides a method for preparing the methanol by coupling gasification of pulverized coal waste boiler and green electro-green hydrogen to realize near-zero carbon emission. Carbon emission in the methanol preparation process only comes from the blow-down gas generated by coal grinding and drying of a coal gasification device and the purge gas generated by methanol synthesis, the carbon emission per ton of methanol is greatly reduced, and the near-zero carbon production of methanol products is realized.
A method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electro-green hydrogen to realize near-zero carbon emission comprises the following steps:
(1) oxygen generated by the air separation device and oxygen generated by the water electrolysis device react with coal in the pulverized coal waste boiler gasification device together to obtain high-temperature synthetic gas, and the high-temperature synthetic gas is sent to a heat recovery device to further recover heat;
(2) the pulverized coal waste boiler gasification device recovers heat of high-temperature synthesis gas through a waste heat boiler and a steam superheater to produce 6.0-13.0 MPaG superheated steam, and the superheated steam is sent to an air separation device to drive an air compressor turbine;
(3) sending the synthesis gas out of the heat recovery device to a purification device, removing only sulfur-containing acid gas without decarburization, and obtaining purified gas containing carbon monoxide, hydrogen and carbon dioxide;
(4) one part of the hydrogen is sent to the hydrogen storage device for storage, and the other part of the hydrogen is sent to the hydrogen compression device; the other part of the electric energy generated by the new energy power generation system is used by other power utilization facilities of the whole plant, and the rest part of the electric energy is sent to the energy storage device for storage;
(5) mixing hydrogen generated by electrolyzing water with purified gas discharged from the purification device to obtain methanol synthesis raw material gas with the hydrogen-carbon molar ratio of 2.0-2.3, and sending the methanol synthesis raw material gas to the methanol synthesis device to produce a methanol product;
(6) and (3) recovering heat in the step (1) and supplying steam which is a byproduct in the step (5) for the whole plant process device and heat tracing.
Furthermore, the pulverized coal waste boiler gasification device adopts a pulverized coal entrained flow bed pressurization gasification technology, and the gasification pressure is 2.5-8.5 MpaG.
Further, the new energy power generation system comprises one or more of photovoltaic, hydraulic, wind, nuclear, biomass, tidal, geothermal and photothermal power generation systems.
Furthermore, the water electrolysis hydrogen production device is composed of a plurality of water electrolysis units, and each unit comprises an electrolytic water tank and a gas purification system.
Further, the energy storage device comprises chemical energy storage or fused salt heat storage type power generation and energy storage.
Further, the chemical energy storage includes lithium ion battery energy storage, sodium ion battery energy storage and lead-acid storage battery energy storage.
By adopting the process, the green power of new energy is used for continuously using electricity for 24 hours in the whole plant, and compared with the traditional method that the electricity is supplied by a power grid (the source is thermal power), the zero carbon emission of a power supply is realized; the problem of traditional coal system methanol route carbon dioxide emission is solved, carbon element utilization ratio in the raw materials coal is close to 100%, carbon element basically all gets into the methanol product, has cancelled the boiler simultaneously, and fuel coal consumption is zero. In the synthesis, the carbon emission in the methanol preparation process only comes from the dry emptying gas of coal grinding of a coal gasification device and the purge gas of methanol synthesis, the carbon emission per ton of methanol is greatly reduced, and the near-zero carbon production of methanol products is realized.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
As shown in fig. 1, an embodiment of the present invention provides a method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electro-green hydrogen to achieve near-zero carbon emission. The method comprises the following steps:
(1) oxygen generated by the air separation device and oxygen generated by the water electrolysis device react with coal in the pulverized coal waste boiler gasification device together to obtain high-temperature synthetic gas, and the high-temperature synthetic gas is sent to a heat recovery device to further recover heat;
(2) the pulverized coal waste boiler gasification device recovers heat of high-temperature synthesis gas through a waste heat boiler and a steam superheater to produce 6.0-13.0 MPaG superheated steam, and the superheated steam is sent to an air separation device to drive an air compressor turbine;
(3) sending the synthesis gas out of the heat recovery device to a purification device, removing only sulfur-containing acid gas without decarburization, and obtaining purified gas containing carbon monoxide, hydrogen and carbon dioxide;
(4) one part of the hydrogen is sent to the hydrogen storage device for storage, and the other part of the hydrogen is sent to the hydrogen compression device; the other part of the electric energy generated by the new energy power generation system is used by other power utilization facilities of the whole plant, and the rest part of the electric energy is sent to the energy storage device for storage;
(5) mixing hydrogen generated by electrolyzing water with purified gas discharged from the purification device to obtain methanol synthesis raw material gas with the hydrogen-carbon molar ratio of 2.0-2.3, and sending the methanol synthesis raw material gas to the methanol synthesis device to produce a methanol product;
(6) and (3) recovering heat in the step (1) and supplying steam which is a byproduct in the step (5) for the whole plant process device and heat tracing.
The new energy power generation system adopts renewable energy sources to generate power, namely green power, and the generated electric energy is used for the water electrolysis device and other power utilization facilities in the whole plant. The hydrogen (green hydrogen) generated by electrolyzing water can partially replace the hydrogen needed by raw coal gas production, and the oxygen (green oxygen) generated by electrolyzing water can partially replace the oxygen needed by coal gasification.
The energy storage device adopts chemical energy storage or fused salt heat storage energy storage, and is adjusted together with green electricity which is a new energy, so that stable and continuous green electricity supply of the whole plant is ensured. The power does not need to be discharged from a power grid, and zero carbon emission of the power is realized.
The waste pulverized coal boiler gasifying device comprises a pulverized coal drying system, a pulverized coal conveying system, a gasifying system, a waste heat boiler, a steam superheater, a synthetic gas ash removing system, an ash water treatment system and an auxiliary system. By adopting a pulverized coal pressure gasification technology, the content of carbon dioxide in the produced crude synthesis gas is low (about 3-10% of dry basis), and meanwhile, due to the supplement of hydrogen prepared by electrolyzing water, a conversion unit in the traditional coal-to-methanol device can be cancelled, so that the generation of redundant carbon dioxide is avoided. The purification unit only carries out desulfurization and does not carry out decarburization, and a small amount of carbon dioxide in the synthesis gas reacts with hydrogen in the methanol synthesis device to finally produce a methanol product, so that nearly 100% of carbon element in the raw material coal is utilized, and nearly zero carbon emission of the raw material coal is achieved.
Meanwhile, the high-pressure superheated steam is byproduct of the pulverized coal waste boiler gasification device and is used for driving the air separation air compressor turbine, so that the matched coal-fired boiler can be omitted, the fuel coal consumption and the carbon emission of the boiler are zero, and the zero carbon emission of the fuel part is realized. Other compressors of the whole plant can be driven by electric power, and the power is from green electricity generated by an upstream new energy power generation system.
The steam used by the process unit and the heat tracing can realize self-production and self-utilization through heat recovery and a byproduct of a methanol synthesis device.
The hydrogen storage device adopts pressure hydrogen storage or liquid hydrogen storage. When the green electricity is insufficient, other electric equipment in the whole plant is preferentially supplied, the water electrolysis device reduces the load or stops the operation, and the hydrogen storage device provides continuous and stable green hydrogen for the downstream synthesis unit.
Claims (6)
1. A method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electro-green hydrogen to realize near-zero carbon emission is characterized by comprising the following steps:
(1) oxygen generated by the air separation device and oxygen generated by the water electrolysis device react with coal in the pulverized coal waste boiler gasification device together to obtain high-temperature synthetic gas, and the high-temperature synthetic gas is sent to a heat recovery device to further recover heat;
(2) the pulverized coal waste boiler gasification device recovers heat of high-temperature synthesis gas through a waste heat boiler and a steam superheater to produce 6.0-13.0 MPaG superheated steam, and the superheated steam is sent to an air separation device to drive an air compressor turbine;
(3) sending the synthesis gas out of the heat recovery device to a purification device, removing only sulfur-containing acid gas without decarburization, and obtaining purified gas containing carbon monoxide, hydrogen and carbon dioxide;
(4) one part of the hydrogen is sent to the hydrogen storage device for storage, and the other part of the hydrogen is sent to the hydrogen compression device; the other part of the electric energy generated by the new energy power generation system is used by other power utilization facilities of the whole plant, and the rest part of the electric energy is sent to the energy storage device for storage;
(5) mixing hydrogen generated by electrolyzing water with purified gas discharged from the purification device to obtain methanol synthesis raw material gas with the hydrogen-carbon molar ratio of 2.0-2.3, and sending the methanol synthesis raw material gas to the methanol synthesis device to produce a methanol product;
(6) and (3) recovering heat in the step (1) and supplying steam which is a byproduct in the step (5) for the whole plant process device and heat tracing.
2. The method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electro-green hydrogen to realize near-zero carbon emission as claimed in claim 1, wherein the pulverized coal waste boiler gasification device adopts pulverized coal entrained-flow bed pressure gasification technology, and the gasification pressure is 2.5-8.5 MpaG.
3. The method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electro-green hydrogen to realize near-zero carbon emission as claimed in claim 1, wherein the new energy power generation system comprises one or more of photovoltaic, hydraulic, wind, nuclear, biomass, tidal, geothermal and photo-thermal power generation systems.
4. The method for preparing methanol by coupling gasification of pulverized coal waste boiler and green electro-green hydrogen to realize near-zero carbon emission as claimed in claim 1, wherein the water electrolysis hydrogen production device is composed of a plurality of water electrolysis units, each unit comprises an electrolysis water tank and a gas purification system.
5. The method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electro-green hydrogen to realize near-zero carbon emission as claimed in claim 1, wherein the energy storage device comprises chemical energy storage or fused salt heat storage type power generation energy storage.
6. The method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electro-green hydrogen to realize near-zero carbon emission as claimed in claim 5, wherein the chemical energy storage comprises lithium ion battery energy storage, sodium ion battery energy storage and lead-acid battery energy storage.
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| CN202111286319.1A CN114394883A (en) | 2021-11-02 | 2021-11-02 | Method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electricity and green hydrogen to achieve near-zero carbon emission |
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| CN116496141A (en) * | 2023-04-14 | 2023-07-28 | 中国天辰工程有限公司 | Green methanol preparation process and system |
| CN118165766A (en) * | 2024-03-21 | 2024-06-11 | 中国天楹股份有限公司 | Off-grid system and method for preparing green methanol by coupling gasified and directly-combusted biomass |
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| CN118165766A (en) * | 2024-03-21 | 2024-06-11 | 中国天楹股份有限公司 | Off-grid system and method for preparing green methanol by coupling gasified and directly-combusted biomass |
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