CN113772672B - Fire flooding oil extraction tail gas carbon emission reduction treatment method - Google Patents
Fire flooding oil extraction tail gas carbon emission reduction treatment method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000000605 extraction Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 238000002407 reforming Methods 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 17
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 230000018044 dehydration Effects 0.000 claims abstract description 14
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 29
- 239000001569 carbon dioxide Substances 0.000 claims description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000012856 packing Methods 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000003795 desorption Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000006276 transfer reaction Methods 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 210000002381 plasma Anatomy 0.000 description 35
- 239000003921 oil Substances 0.000 description 14
- 239000012670 alkaline solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- B01D53/26—Drying gases or vapours
-
- 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
- B01D53/26—Drying gases or vapours
- B01D53/266—Drying gases or vapours by filtration
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/28—Ammonium phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0861—Methods of heating the process for making hydrogen or synthesis gas by plasma
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The utility model relates to a fire flooding oil extraction tail gas carbon emission reduction treatment method, which comprises the following steps: (1) removing water from the fireflood tail gas through a dehydration unit; (2) The tail gas after water removal is reacted by a plasma reforming unit to generate water gas, and hydrogen in the water gas is reacted with nitrogen to generate ammonia; (3) Ammonia in the tail gas is subjected to the action of a cooling and dedusting unit to generate ammonium salt, and the solvent is removed to obtain ammonium salt solid; (4) removing residual acid from the reformed tail gas through a deacidification unit; (4) The deacidification tail gas is dehydrated and adsorbed by a pressure swing adsorption unit, and nitrogen and carbon monoxide are separated; the method can reduce carbon emission, recycle tail gas, and solve the problem that pipelines are frozen due to condensation of water vapor in winter.
Description
Technical Field
The utility model relates to the field of petroleum exploitation tail gas treatment, in particular to a carbon emission reduction method for tail gas of fireflood oil exploitation.
Background
The fire flooding oil extraction is to inject air into an underground oil layer by adopting a high-pressure fan and ignite and burn the air, and heat and smoke generated in the burning process push crude oil to a production well from a steam injection well, so that the short-distance displacement exploitation of the crude oil is realized, the fire flooding oil extraction is particularly suitable for thick oil exploitation, and the fire flooding oil extraction has the advantages of high heat efficiency utilization rate, high oil extraction rate, low exploitation cost, wide application range of an oil field and the like.
The fireflood tail gas contains CH besides nitrogen 4 、CO 2 、H 2 S, etc.
The fire flooding tail gas also contains a large amount of water vapor, and if the fire flooding tail gas is not treated, the phenomenon of freezing and blocking of a pipeline can occur in winter, so that the system is pressurized, and the efficiency of fire flooding oil extraction is seriously affected.
The plasma is in a fourth state of existence of substances, has the characteristics of active particles, high temperature and high energy density, can lead two substances to be difficult to react quickly by chemical reaction under the general condition, increases the chemical reaction rate, saves the reaction cost and the like, and is gradually applied to chemical reaction.
CN 212327831U adopts a dehydration-desulfurization-pressure swing adsorption process to treat fireflood tail gas, and recovers methane for recycling, but carbon dioxide in fireflood is discharged into environment, thus increasing carbon emission; CN 108392958A adopts cyclone separator-cooling-desulfurizing process to treat tail gas, so that the problems of liquid accumulation and freeze blocking of tail gas pipeline are solved, but the carbon dioxide and methane in tail gas are not treated, and the risk of environmental greenhouse effect is increased.
Disclosure of Invention
In order to overcome the defects in the prior art, the technical problem to be solved by the utility model is to provide a treatment method for reducing carbon emission of tail gas of fireflood oil extraction, which not only can solve the problem that a pipeline is frozen due to condensation of water vapor in winter, but also can reduce dissociation of water into oxygen in plasma reforming, prevent a generation source of carbon dioxide, reduce carbon emission and simultaneously recycle the tail gas.
The specific technical scheme is as follows:
A. removing water from the fireflood tail gas through a dehydration unit;
B. the tail gas after water removal is reacted by a plasma reforming unit to generate water gas, and hydrogen in the water gas is reacted with nitrogen to generate ammonia;
C. ammonia in the tail gas acts on the cooling and dedusting unit to generate ammonium salt;
D. removing residual acid from the reformed tail gas through a deacidification unit;
E. the acid-removing tail gas is dehydrated by a pressure swing adsorption unit, and nitrogen and carbon monoxide are separated.
In the step A, the dehydration unit comprises a gas-liquid separator and a precise filter, tail gas discharged from a fire flooding oil extraction inlet is sequentially connected with the gas-liquid separator and the precise filter, the tail gas enters the plasma reforming unit after being dehydrated by the gas-liquid separator 1 and the precise filter 3, and moisture removed by the gas-liquid separator 1 and the precise filter 3 is converged into the sewage tank 2 for harmless treatment.
Further, the temperature of the gas-liquid separator 1 is 10 to 50 ℃, preferably 35 ℃, and the pressure is 80 to 600 KPa, preferably 100 to 250 KPa.
In the step B, the plasma reforming unit comprises a carbon dioxide reforming tower 4, a plasma torch 6, a plasma power supply 5, a deionized water tank 8, a deionized water circulating pump 7 and an air cooler 9. The dehydrated tail gas enters a carbon dioxide reforming tower 4, carbon dioxide and methane in the tail gas react under the catalysis of plasma active particles to generate water gas (carbon monoxide is the main component), in order to improve the gas-gas reaction efficiency, the tail gas enters the carbon dioxide reforming tower 4 in a tangential rotational flow mode, plasma torches 6 are arranged at positions which are opposite to tangential directions and are 200-500 mm higher than the section of the tail gas inlet (relative to the air inlet direction of the tail gas), so that plasmas enter the carbon dioxide reforming tower 4, the tail gas and plasmas are fully mixed in the tower, the carbon dioxide and methane in the tail gas react under the catalysis of the plasma active particles to generate carbon monoxide and hydrogen, and the hydrogen reacts with nitrogen plasmas to generate ammonia. The plasma torch 6 adopts nitrogen as working medium gas, plasma cooling adopts deionized water for cooling, the deionized water enters a deionized water tank 8 after heat exchange between a water chamber of the plasma torch and an electric arc channel of the plasma torch, and the deionized water is pumped into an air cooler 9 through an ion circulating water pump 7 and is sent into the plasma torch 6 after air cooling heat exchange.
Further, the average temperature of the plasma torch is 2000-4000 ℃, preferably 2500-3000 ℃.
In the step C, the cooling and dedusting unit comprises a packed tower 10, an acid liquor tank 11, an acid liquor pump 12 and a centrifuge 14. The reformed tail gas enters a packing tower 10 to carry out mass transfer and heat transfer with an acidic solution at the upper end of the packing tower in a countercurrent way, alkaline gas (mainly ammonia gas) in the tail gas is absorbed to form an ammonium salt solution, after the ammonium salt is saturated, the solvent is removed, ammonium salt solid is obtained, and the separated liquid is conveyed to an acid liquor tank.
Further, the acid liquid in the packed tower comprises one or more of the following acids, sulfuric acid, phosphoric acid, preferably sulfuric acid.
Further, the concentration of the sulfuric acid solution is in the range of 1 to 20 mol/L, preferably 5 to 10 mol/L.
Further, the process of obtaining ammonium salt solids includes removing liquid from saturated ammonium salt and retaining solid part, and includes but is not limited to: conventional means for removing liquid such as filtration and centrifugation may be used alone or in combination.
The deacidification unit in the step D comprises an alkaline washing tower 15, an alkaline solution tank 16 and an alkaline solution pump 17, the tail gas is cooled to normal temperature through a packing tower 10 and then is sent to the deacidification unit to remove residual acid gas of the tail gas, the alkaline washing tower 15 also adopts the packing tower, the tail gas carries out mass transfer and heat transfer reaction with alkaline solution in a countercurrent mode, alkaline solution absorbing residual acid flows into the alkaline solution tank 16 from the gravity and then is sent to the alkaline washing tower 15 through the alkaline solution pump to circularly spray and wash the residual acid, a PH meter is arranged on the alkaline solution tank 16, when the PH value is reduced to be neutral, a part of liquid is discharged, and new alkaline solution is supplemented into the tank.
Further, the alkali in the alkali wash tower 15 may be selected from one or several of the following: potassium hydroxide, sodium hydroxide, calcium hydroxide, preferably calcium hydroxide.
In step E, the pressure swing adsorption unit includes a compressor 18, a dehydration tank 19, and an adsorption tank 20. The tail gas after absorbing the residual acid directly enters a pressure swing adsorption unit, the deacidified tail gas is pressurized by a compressor 18 and then is sent to a dehydration tank 19, the tail gas is dehydrated in the dehydration tank 19 and then enters the pressure swing adsorption tank 20, the pressure swing adsorption is operated by adopting two towers, one tower is in a feeding adsorption state, the other tower is in a desorption state, and the whole process is completed by adsorption, pressure equalizing and depressurization, desorption and pressure equalizing and pressure boosting. And (3) taking one part of desorbed nitrogen as working medium gas of the plasma torch, exhausting and discharging the other part of gas, and delivering the desorbed carbon monoxide to a carbon monoxide storage tank for recycling.
Further, in the pressure swing adsorption process, the pressure range is 400-800 KPa, preferably 500-600 KPa.
Compared with the prior art, the technical scheme of the utility model has the remarkable beneficial effects that:
(1) According to the utility model, methane and carbon dioxide in the fireflood tail gas are subjected to plasma reforming to obtain carbon monoxide and ammonium salt, and the carbon monoxide and the ammonium salt can be recycled, so that the aim of reducing greenhouse gas emission is fulfilled.
(2) The dehydration unit added in the utility model can timely remove the moisture in the fireflood tail gas, keep the ventilation pipeline smooth even in winter, reduce the dissociation of water into oxygen in plasma reforming and stop the generation source of carbon dioxide.
(3) The ion reforming unit adopts a deionized water circulating water supply system, so that cooling water can be recycled, and the waste of water resources is reduced.
(4) In the specific embodiment of the utility model, the deacidification unit not only can remove hydrogen sulfide in the tail gas, but also can remove sulfuric acid gas carried out in the cooling and dedusting unit.
Drawings
FIG. 1 is a schematic diagram of the structure of the present utility model;
FIG. 2 is a schematic diagram of a plasma reforming unit;
FIG. 3 is a schematic diagram of a cooling and dedusting unit;
fig. 4 is a schematic structural diagram of the deacidification unit.
1-a gas-liquid separator; 2-a sewage tank; 3-a precision filter; a 4-carbon dioxide reforming tower; 5-plasma power supply; a 6-plasma torch; 7-deionized water pump; 8-a deionized water tank; 9-an air cooler; 10-packing tower; 11-an acid liquor tank; 12-an acid liquid pump; 13-a concentrate pump; 14-a centrifuge; 15-an alkaline washing tower; 16-an alkali solution tank; 17-an alkaline solution pump; 18-a compressor; 19-a dehydration tank; 20-an adsorption tank; 21-a tail gas conveying pipe; 22-nitrogen gas discharge pipe.
Detailed Description
The embodiments of the present utility model will be described below with reference to the accompanying drawings, it being understood that the embodiments described herein are for illustration and explanation of the present utility model only, and are not intended to limit the present utility model.
Fire flooding is to artificially inject high-pressure air into the stratum continuously and ignite the air to form a burning zone, so that the purposes of crude oil cracking, distillation and viscosity reduction are achieved. The oxygen in the air is consumed to form flue gas which is discharged through a production well, and the components of the flue gas mainly comprise nitrogen, methane, carbon dioxide, carbon monoxide, ethane, propane, hydrogen sulfide, saturated steam and the like, wherein the nitrogen, the methane and the carbon dioxide account for more than 97 percent except the saturated steam. The tail gas composition of a fireflood well of a certain oil field is shown in table 1:
。
from the tail gas components, the water vapor accounts for 19.1% of the tail gas, and the water vapor has influence on the tail gas treatment: in winter, the water vapor condenses when cooled, and as the temperature decreases, the water vapor condenses into ice to cause pipeline blockage. Therefore, the water vapor in the tail gas needs to be separated.
The tail gas discharged from the fireflood oil extraction inlet is sequentially connected with a gas-liquid separator 1 and a precise filter 3 to separate the water vapor in the tail gas, the temperature of the gas-liquid separator is 35 ℃, the pressure is 175 KPa, and the water content (water content is more than 2.5 g/Nm) in the tail gas can be reduced 3 ) Down to < 0.5g/Nm 3 . The water removed by the gas-liquid separator 1 and the precise filter 3 is subjected to innocent treatment.
The dehydrated tail gas enters a carbon dioxide reforming tower 4, carbon dioxide and methane in the tail gas react under the catalysis of plasma active particles to generate carbon monoxide and hydrogen, the hydrogen further reacts with nitrogen plasma to generate ammonia, in order to improve the gas-gas reaction efficiency, the tail gas enters the carbon dioxide reforming tower 4 in a tangential rotational flow mode, plasma torches (the average temperature of the plasma torches is 3000 ℃) are arranged at positions which are tangential in opposite directions and 300mm higher than the section of an inlet of the tail gas (relative to the air inlet direction of the tail gas), so that the plasma enters the carbon dioxide reforming tower 4, and the tail gas and the plasma are fully mixed in the tower. The plasma torch 6 adopts nitrogen as working medium gas, plasma cooling adopts deionized water for cooling, the deionized water enters a deionized water tank 8 after heat exchange between a water chamber of the plasma torch 6 and an electric arc channel of the plasma torch, and the deionized water is pumped into an air cooler 9 through an ion circulating water pump 7 and is sent into the plasma torch 6 after air cooling heat exchange.
The reformed tail gas enters a packing tower 10 to be countercurrent to 7.5 mol/L sulfuric acid solution at the upper end of the packing tower for mass transfer and heat transfer on the packing tower 10, ammonia gas in the tail gas is absorbed to form a solution of ammonium sulfate and ammonium bisulfate, the solution is sent to a centrifugal machine 14 after being saturated, ammonium sulfate and ammonium bisulfate solids are thrown out for bagging under the action of high-speed centrifugal force of the centrifugal machine 14, and separated liquid is sent to an acid liquor tank 11.
The tail gas is cooled to normal temperature by a packing tower 10 and then is sent to a deacidification unit to remove residual acid gas in the cooling and dedusting unit, the residual acid is mainly hydrogen sulfide and sulfuric acid, a packing tower is also adopted by an alkaline washing tower 15, saturated calcium hydroxide solution is used as alkaline liquid by alkaline liquid, the tail gas carries out mass transfer and heat transfer reaction with the alkaline liquid in a countercurrent mode, the alkaline liquid absorbing the residual acid flows into an alkaline liquid tank 16 from the gravity and then is sent to the alkaline washing tower 15 through an alkaline liquid pump 17 to circularly spray and wash the residual acid, a pH meter is arranged on the alkaline liquid tank 16, and when the pH value is reduced to be neutral, a part of liquid is discharged, and new alkaline liquid is supplemented into the tank.
The tail gas after absorbing the residual acid directly enters a pressure swing adsorption unit, the deacidified tail gas is pressurized by a compressor 18 and then is sent to a dehydration tank 19, the tail gas is dehydrated in the dehydration tank 19 and then enters a pressure swing adsorption tank 20, the pressure swing adsorption is operated by two towers, one tower is in a feeding adsorption state, the other tower is in an analysis state, the whole process is completed by adsorption, pressure equalizing and depressurization, desorption and pressure equalizing and pressure boosting, and the pressure swing range is 500-600 KPa. Part of desorbed nitrogen is used as working medium gas of the plasma torch 6, the other part of the desorbed nitrogen is exhausted and discharged, and the desorbed carbon monoxide is sent to a carbon monoxide storage tank for recycling.
After the treatment of the steps, the discharged tail gas meets the emission requirements of the 'integrated emission standard of atmospheric pollutants' GB 16297-1996 and the 'emission standard of malodorous pollutants' GB 14554-1993 in the second-class region, and the components and the ratio of the discharged tail gas are shown in Table 2.
The foregoing is a further detailed description of the utility model in connection with specific embodiments, and it is not intended that the utility model be limited to those specific embodiments. It will be apparent to those skilled in the art that several deductions or substitutions may be made without departing from the spirit of the utility model, and these shall be considered to be within the scope of the utility model.
Claims (10)
1. The fire flooding oil extraction tail gas carbon emission reduction treatment method is characterized by comprising the following steps of:
A. dewatering the fireflood tail gas through a dewatering unit;
B. the tail gas after water removal is reacted by a plasma reforming unit to generate water gas, and hydrogen in the water gas is reacted with nitrogen to generate ammonia;
C. ammonia in the tail gas is subjected to the action of a cooling and dedusting unit to generate ammonium salt, and the solvent is removed to obtain ammonium salt solid;
D. removing residual acid from the reformed tail gas through a deacidification unit;
E. the acid-removing tail gas is dehydrated and adsorbed by a pressure swing adsorption unit, and nitrogen and carbon monoxide are separated.
2. The method according to claim 1, wherein the dehydration unit in step a comprises a gas-liquid separator (1), a sewage tank (2), a fine filter (3); the plasma reforming unit in the step B comprises a carbon dioxide reforming tower (4), a plasma power supply (5), a plasma torch (6), a deionized water circulating pump (7), a deionized water tank (8) and an air cooler (9); the cooling and dedusting unit in the step C comprises a packing tower (10), an acid liquor tank (11), an acid liquor pump (12), a concentrate pump (13) and a centrifuge (14); the deacidification unit in the step D comprises an alkaline washing tower (15), an alkaline liquor tank (16), an alkaline liquor pump (17), a compressor (18), a dehydration tank (19), an adsorption tank (20), a tail gas conveying pipe (21) and a nitrogen discharge pipe (22).
3. The method according to claim 1 or 2, wherein the temperature of the gas-liquid separator (1) in step a is 10-50 ℃; the pressure is 80-600 KPa.
4. The method of claim 1 or 2, wherein in the step B, the tail gas and the plasma are fully mixed in a carbon dioxide reforming tower (4), carbon dioxide and methane in the tail gas react under the catalysis of active particles of the plasma to generate carbon monoxide and hydrogen, the hydrogen further reacts with nitrogen to generate ammonia, the average temperature of the plasma torch is 2000-4000 ℃, and working medium gas adopted by the plasma torch is nitrogen.
5. The method according to claim 1 or 2, wherein in the step B, the tail gas enters the carbon dioxide reforming tower (4) in a tangential swirling manner, the plasma torch (6) is arranged in a position which is opposite to the tangential direction and higher than the cross section of the tail gas inlet so that the plasma enters the carbon dioxide reforming tower (4), and the distance between the plasma torch and the cross section of the tail gas inlet is 200-500 mm.
6. The method according to claim 1 or 2, wherein the reformed tail gas in the step C enters a packing tower (10) to carry out mass transfer and heat transfer with acid liquor at the upper end of the packing tower in a countercurrent manner, alkaline gas in the tail gas is absorbed to form ammonium salt solution, the ammonium salt solution is sent to a centrifuge (14) after being saturated, ammonium salt solid is thrown out for bagging under the action of the centrifuge (14), and the separated liquor is sent to an acid liquor tank (11), wherein the acid liquor is sulfuric acid solution or phosphoric acid solution; the concentration range of the acid liquor is 1-20 mol/L.
7. The method according to claim 1 or 2, characterized in that in step D, the tail gas and the alkali liquor are subjected to mass transfer and heat transfer reaction, the tail gas and the alkali liquor flow in opposite directions, the alkali liquor absorbing the residual acid flows into the alkali liquor tank (16) from the gravity and is then conveyed to the alkali liquor washing tower (15) through the alkali liquor pump (17) to circularly spray and wash the residual acid, a pH meter is arranged on the alkali liquor tank (16), when the pH value is reduced to be neutral, a part of liquid is discharged, and new alkali liquor is supplemented into the tank, wherein the alkali liquor is potassium hydroxide solution or sodium hydroxide solution or calcium hydroxide solution.
8. The method according to claim 1 or 2, wherein the deacidified tail gas is pressurized by a compressor (18) and then sent to a dehydration tank (19), the tail gas is dehydrated in the dehydration tank (19) and then enters a pressure swing adsorption tank (20), the pressure swing adsorption is operated by using 2 towers, one tower is in a feeding adsorption state, the other tower is in a desorption state, the whole process of the method is completed by adsorption, pressure equalizing and depressurization, desorption and pressure equalizing and pressurization, and the pressure range of the pressure swing adsorption process is 400-800 KPa.
9. The method of claim 8, wherein a portion of the desorbed nitrogen is used as the working fluid gas for the plasma torch and another portion of the desorbed nitrogen is purged and vented; and delivering the desorbed carbon monoxide to a carbon monoxide storage tank for recycling.
10. The method of claim 1, wherein the fireflood tail gas comprises carbon dioxide, nitrogen, water, methane, oxygen, carbon monoxide, hydrogen sulfide, ethane, propane.
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