CN113828145A - Method for recycling and treating tail gas of coking plant - Google Patents
Method for recycling and treating tail gas of coking plant Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004939 coking Methods 0.000 title abstract description 13
- 238000004064 recycling Methods 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010926 purge Methods 0.000 claims abstract description 21
- 239000000571 coke Substances 0.000 claims abstract description 16
- 238000000855 fermentation Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000006200 vaporizer Substances 0.000 claims abstract description 16
- 238000010564 aerobic fermentation Methods 0.000 claims abstract description 14
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 13
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003860 storage Methods 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 4
- 230000023556 desulfurization Effects 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims 2
- 238000007599 discharging Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 81
- 239000007789 gas Substances 0.000 abstract description 71
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 42
- 239000001569 carbon dioxide Substances 0.000 abstract description 31
- 229910052799 carbon Inorganic materials 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012460 protein solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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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
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- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P21/00—Preparation of peptides or proteins
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Abstract
The application discloses a recovery treatment method for tail gas of a coking plant, which sequentially comprises the following steps: the S1 coke oven gas is sequentially subjected to desulfurization, methane conversion, methanol synthesis and methanol rectification to obtain methanol, and S2 liquid CO2After being stored in a storage tank, the CO is gasified by adopting a water bath type vaporizer to form gas CO2(ii) a S3 gaseous CO obtained in step S22And at the time of methanol synthesis in step S1And (3) mixing and pressurizing the purge gas by a mixed gas compressor, and then sequentially performing anaerobic fermentation, aerobic fermentation, concentration and drying to obtain the biological protein powder. The invention aims at the problems that coke oven gas of a coking company has more hydrogen and less carbon, a large amount of hydrogen in the purge gas of the coke oven is wasted by burning after methanol is synthesized, and meanwhile, a part of carbon dioxide is generated after a part of carbon monoxide in the purge gas is burnt, and the carbon dioxide is finally discharged to the atmosphere, so that the discharge pressure of environmental carbon is caused, and on the other hand, carbon is not reasonably utilized and certain social value is generated.
Description
Technical Field
The application relates to tail gas treatment of a coking plant, in particular to a recovery treatment method of tail gas of the coking plant.
Background
The main components of the coke oven gas of a coking enterprise are hydrogen (55 v% -60 v%), methane (23 v% -27 v%), carbon monoxide (5 v% -8 v%), carbon dioxide (1.5 v% -3 v%), and nitrogen (3 v% -7 v%), and considering that the hydrogen-carbon ratio of the coke oven gas is higher, the common coke oven gas is used for manufacturing methanol, even if the hydrogen surplus phenomenon occurs in the process, the hydrogen content in the purge gas is higher, and in order to solve the problem, the hydrogen of the purge gas is recycled at the same time, a coking plant has two solutions, one is to arrange a pressure swing adsorption device and recycle the hydrogen of the purge gas; the other method is to pressurize the carbon dioxide gas in the methanol rectification process and return the carbon dioxide gas to the methanol synthesis device again. The two methods fundamentally do not solve the problems of environmental protection and energy conservation. The first method pressure swing adsorption unit cannot effectively recycle the carbon part; the carbon supplemented by the second method is carbon dioxide which needs to be released in a methanol rectification system, and the amount of the supplemented carbon is insufficient, so that the closed cycle operation is unstable. The purge gas cannot find an effective utilization way, and certain loss is caused to enterprises.
Disclosure of Invention
The invention aims to provide a method for recovering and treating tail gas of a coking plant, aiming at the emission of carbon dioxide which is gradually increased in the atmosphere at present, the carbon dioxide discharged in the industrial production process and the excessive hydrogen in the process of preparing methanol from coke oven gas are combined to produce the biological protein powder, so that the environment is protected, the energy is saved, the emission is reduced, and the biological protein powder with high added value is produced again. The novel coke oven gas process can realize clean, efficient and cyclic utilization and reduce the emission of carbon. Meanwhile, carbon dioxide generated in the production process of chemical engineering, power plants and coking plants can be recycled. The carbon is collected and utilized in the carbon, and the harm to the environment is reduced.
In order to achieve the above object, the present invention provides the following technical solutions.
The embodiment of the application discloses a recovery treatment method for tail gas of a coking plant, which sequentially comprises the following steps:
s1 the coke oven gas is sequentially subjected to desulfurization, methane conversion, methanol synthesis and methanol rectification to obtain methanol,
s2 gasifying the liquid CO2 into gas CO2 by a water bath type vaporizer after being stored by a storage tank;
s3, mixing and pressurizing the CO2 obtained in the step S2 and purge gas obtained in the step S1 during methanol synthesis by a mixed gas compressor, and then sequentially performing anaerobic fermentation, aerobic fermentation, concentration and drying to obtain the biological protein powder.
Preferably, in the above-mentioned method for recovering and treating tail gas from a coke-oven plant, CO2 vent gas generated during the rectification of methanol in step S1 is simultaneously introduced into the mixed gas compressor for mixing and pressurizing.
Preferably, in the above-mentioned method for recovering and treating tail gas from a coke-oven plant, a small amount of purge gas generated by anaerobic fermentation in step S3 is directly combusted and exhausted, and a byproduct low-pressure steam is generated.
Preferably, in the method for recovering and treating tail gas from a coke-oven plant, the cold energy generated by the gasification in the water-bath vaporizer in step S2 is used for the aerobic fermentation in step S3 by circulating chilled water.
Preferably, in the above method for recovering and treating tail gas from a coke-oven plant, the heat generated by aerobic fermentation in step S3 is gasified by circulating chilled water in the water bath vaporizer in step S2.
Compared with the prior art, the technical scheme of the invention has the advantages that: the method aims at the problems that coke oven gas of a coking company has more hydrogen and less carbon, a large amount of hydrogen in purge gas of the coke oven is wasted by burning after methanol is synthesized, meanwhile, a part of carbon dioxide is generated after a part of carbon monoxide in the purge gas is burnt, and the carbon dioxide is finally discharged to the atmosphere, so that the environmental carbon discharge pressure is caused, and on the other hand, carbon is not reasonably utilized and certain social value is generated.
The invention fully utilizes the redundant hydrogen with more hydrogen in the coking plant by a mode of 'carbureting and reasonably configuring hydrogen-carbon ratio', reasonably utilizes the hydrogen and the carbon to generate the biological protein powder, and effectively and fully recycles the carbon, thereby achieving the purposes of environmental protection and generating certain economic value and social benefit. According to the method, carbon elements are supplemented into a production system in a carbon dioxide form through equipment such as a carbon supplementing device, the carbon dioxide is delivered to a device boundary area in a liquid state, under the normal production condition, the pressure in a liquid carbon dioxide storage tank is maintained to be stable through a self-pressurization system, the liquid carbon dioxide is gasified through a water bath type gasifier and then delivered to a purge gas compressor to be mixed with the purge gas of a coke oven for pressurization, the pressurized mixed gas is subjected to anaerobic fermentation and aerobic fermentation to generate the protein liquid, and the protein liquid is purified and dried to produce the biological protein powder with high added value.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a process for recovering and treating tail gas from a coke plant according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described in detail below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to fig. 1, the method for recovering and treating tail gas of a coke-oven plant sequentially comprises the following steps:
s1 the coke oven gas is sequentially subjected to desulfurization, methane conversion, methanol synthesis and methanol rectification to obtain methanol,
s2 gasifying the liquid CO2 into gas CO2 by a water bath type vaporizer after being stored by a storage tank;
s3, mixing and pressurizing the CO2 obtained in the step S2 and purge gas obtained in the step S1 during methanol synthesis by a mixed gas compressor, and then sequentially performing anaerobic fermentation, aerobic fermentation, concentration and drying to obtain the biological protein powder.
And simultaneously feeding CO2 vent gas generated in the rectification of the methanol in the step S1 into a mixed gas compressor for mixing and pressurizing. The small amount of purge gas generated by anaerobic fermentation in step S3 is directly exhausted by combustion, and byproduct low-pressure steam is generated. The cold energy generated during the gasification of the water bath vaporizer in step S1 is used for the aerobic fermentation in step S3 by circulating chilled water. The heat generated by the aerobic fermentation in the step S3 is used for the gasification of the water bath type vaporizer in the step S1 through the circulating chilled water.
The invention provides a method for producing biological protein powder by methanol synthesis purge gas and carbon dioxide low pressure of coke oven gas in a coke-oven plant, which can effectively recover the purge gas and recycle carbon, reduce carbon emission and produce by-product products with high added value.
The invention has the advantages that:
1. and a liquid carbon dioxide supplement mode is adopted, so that the hydrogen-carbon ratio of the device is easy to control and adjust.
2. The liquid carbon dioxide is changed into carbon dioxide gas by adopting a liquid carbon dioxide storage tank and a water bath type vaporizer, and the part can generate certain cold energy which is taken away by circulating chilled water.
3. And a mixed gas compressor is adopted, and before pressurization, purge gas and carbon dioxide are mixed in advance and then enter the mixed gas compressor.
4. The pressurized anaerobic fermentation device is adopted, and the mixed gas is pressurized by the mixed gas compressor, so that the solubility of the effective gas in the liquid is improved, and the reaction efficiency is improved.
5. The carbon dioxide water bath type vaporizer generates cold energy which is supplied to aerobic fermentation through circulating chilled water, fermentation heat generated by the aerobic fermentation is brought to the water bath type vaporizer through the circulating chilled water, energy is utilized in a matching mode, and energy is saved and consumption is reduced.
6. The pressure range of the pressurized anaerobic fermentation device is 0.5-0.8 MPa, preferably 0.8MPa, and the power consumption is relatively low.
7. Adjusting the hydrogen-carbon ratio H2/CO2=2, the final emission of 1kmol of incorporated carbon dioxide component is 0.1kmol carbon dioxide.
8. Carbon monoxide in the gaseous component also participates in the reaction. The final emission of 1kmol of carbon monoxide was 0.1kmol of carbon dioxide.
The following description will be made by using an embodiment
Off-gas 8117Nm from methanol synthesis plant of coke-oven plant containing 52v% hydrogen, 11v% carbon monoxide, 8v% carbon dioxide and 29v% nitrogen3H, entering a device boundary area through a gas pipeline; the liquid carbon dioxide content was 995Nm3And h, the gas enters a water bath type vaporizer from an outlet pipeline of a liquid carbon dioxide storage tank, the carbon dioxide passing through the water bath type vaporizer is heated and vaporized into a gas state by water, the carbon dioxide gas and purge gas are mixed and then enter a mixed gas compression system, the compressed mixed gas at normal pressure has the pressure of 0.8MPa, the compressed mixed gas enters an anaerobic fermentation reaction to generate an intermediate product, the intermediate product discharged from the bottom of the anaerobic fermentation tank is 2.5wt% of acetic acid, unreacted gas is arranged at the top of the anaerobic fermentation tank, the gas enters a boiler combustion system, and is directly discharged after combustion, and low-pressure steam is byproduct. The intermediate product from the bottom of the anaerobic fermentation tank is aerobically fermented to generate 4wt% protein solution, and the fermentation heat generated in the reaction process of the aerobic fermentation tank can be taken away by using the cold energy of the liquid carbon dioxide water bath type vaporizer, and the process is a continuous operation process. The 4wt% protein solution is purified, concentrated and dried in a series of ways, and finally 95wt% biological protein powder can be obtained, about 1298 ten thousand tons of 95% protein powder can be produced every year, and 3587 ten thousand tons of carbon dioxide emission can be reduced every year.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (5)
1. A recovery treatment method for tail gas of a coke-oven plant is characterized by sequentially comprising the following steps:
s1 the coke oven gas is sequentially subjected to desulfurization, methane conversion, methanol synthesis and methanol rectification to obtain methanol,
s2 liquid CO2After being stored in a storage tank, the CO is gasified by adopting a water bath type vaporizer to form gas CO2；
S3 gaseous CO obtained in step S22And (4) mixing and pressurizing the purge gas obtained in the step (S1) during methanol synthesis by using a mixed gas compressor, and then sequentially performing anaerobic fermentation, aerobic fermentation, concentration and drying to obtain the biological protein powder.
2. The method of claim 1, wherein the CO produced during the rectification of methanol in step S1 is recovered from the tail gas of the coke-oven plant2And simultaneously discharging the air into the mixed air compressor for mixing and pressurizing.
3. The coke-oven plant tail gas recovery processing method as claimed in claim 1, characterized in that the small amount of purge gas generated by anaerobic fermentation in step S3 is directly combusted and exhausted, and byproduct low-pressure steam is generated.
4. The method of claim 1, wherein the cold energy generated by the gasification of the water bath vaporizer in step S2 is used for the aerobic fermentation in step S3 by circulating chilled water.
5. The coke-oven plant tail gas recovery processing method as claimed in claim 1, wherein the heat generated by aerobic fermentation in step S3 is used for gasification in step S2 by circulating chilled water in the water bath vaporizer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115819313A (en) * | 2022-05-17 | 2023-03-21 | 重庆市中润化学有限公司 | Process for producing NMP (N-methyl pyrrolidone) and capable of realizing hydrogen recycling |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819313A (en) * | 2022-05-17 | 2023-03-21 | 重庆市中润化学有限公司 | Process for producing NMP (N-methyl pyrrolidone) and capable of realizing hydrogen recycling |
| CN115819313B (en) * | 2022-05-17 | 2024-04-02 | 重庆中润新材料股份有限公司 | NMP production process capable of realizing hydrogen recycling |
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