CN113117454B - Processing method of storage tank breathing gas - Google Patents
Processing method of storage tank breathing gas Download PDFInfo
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- CN113117454B CN113117454B CN201911424107.8A CN201911424107A CN113117454B CN 113117454 B CN113117454 B CN 113117454B CN 201911424107 A CN201911424107 A CN 201911424107A CN 113117454 B CN113117454 B CN 113117454B
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- gas
- catalytic oxidation
- storage tank
- oxidation unit
- cyclodextrin
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- 230000029058 respiratory gaseous exchange Effects 0.000 title claims abstract description 38
- 238000003672 processing method Methods 0.000 title description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 74
- 230000003647 oxidation Effects 0.000 claims abstract description 73
- 230000003197 catalytic effect Effects 0.000 claims abstract description 69
- 238000010521 absorption reaction Methods 0.000 claims abstract description 54
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 40
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 40
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000002250 absorbent Substances 0.000 claims abstract description 14
- 230000002745 absorbent Effects 0.000 claims abstract description 14
- 238000003795 desorption Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 100
- 239000002912 waste gas Substances 0.000 claims description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 26
- 229920000858 Cyclodextrin Polymers 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 14
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical group O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 14
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- 239000003344 environmental pollutant Substances 0.000 claims description 8
- 231100000719 pollutant Toxicity 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 7
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052878 cordierite Inorganic materials 0.000 claims description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 3
- 239000001116 FEMA 4028 Substances 0.000 claims description 3
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 3
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 3
- 229960004853 betadex Drugs 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 230000000241 respiratory effect Effects 0.000 abstract description 15
- 230000007774 longterm Effects 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000004880 explosion Methods 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
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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
- B01D53/14—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 absorption
- B01D53/1487—Removing organic 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
- B01D53/14—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 absorption
-
- 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
- B01D53/14—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 absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
- B01D53/14—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 absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing 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
- B01D53/46—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
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—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
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Gas Separation By Absorption (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a treatment method of storage tank respiratory gas, which is to introduce storage tank respiratory gas into an absorption tower, spray absorbent for treatment, and the treated gas enters a catalytic oxidation unit, when the storage tank has no respiratory gas or the gas quantity is low, the absorption liquid is thermally regenerated by adopting high-temperature purified gas generated by the catalytic oxidation unit, and the generated hydrocarbon-containing desorption gas enters the catalytic oxidation unit for treatment, so that the safe and stable operation of the catalytic oxidation unit is maintained. The method combines the characteristic of unorganized discharge of the breathing gas of the storage tank, avoids the impact of the fluctuation of the breathing gas quantity and the concentration of hydrocarbon substances in the breathing gas on the catalytic oxidation, reduces the scale of the catalytic oxidation device, and ensures the long-term safe and stable operation of the catalytic oxidation unit.
Description
Technical Field
The invention belongs to the field of gas absorption, and particularly relates to a treatment method of storage tank breathing gas.
Background
The chemical storage tank is used as a main unstructured VOCs waste gas source in petrochemical industry, waste gas dissipation is mainly caused by respiratory loss, wherein the respiratory loss refers to steam escape caused by temperature and pressure changes, and storage tank respiratory gas comprises large breath and small breath. Because the concentration of VOCs in the escaping waste gas of the storage tank is higher, and some storage tanks contain sulfides, direct discharge can cause serious pollution to the surrounding environment, and physical and mental health of enterprise staff and residents can be influenced. Thus, the discharged breathing gas needs to be collected and treated. However, due to the high concentration and large fluctuation of VOCs in the storage tank respiratory gas, the safe and stable operation of the waste gas treatment device is not facilitated, if the waste gas treatment device is treated by adopting a direct thermal oxidation technology, a large amount of air conditioning concentration is required to be supplemented, and the device is frequently stopped in an over-temperature interlocking way due to the high concentration of the waste gas, even when the concentration of the storage tank respiratory gas reaches the explosion limit range of organic matters, the flash explosion accident can occur due to improper operation.
CN109939534a discloses a device for treating VOCs waste gas by coupling adsorption concentration and catalytic combustion, which is suitable for treating VOCs waste gas with large air volume and low concentration, and adopts adsorption as a control means for emission of VOCs waste gas, and adopts adsorption desorption gas to treat the waste gas by a catalytic combustion device, and the hot tail gas of catalytic combustion is used as adsorption pyrolysis desorption gas. However, adsorption tends to have a certain application range for hydrocarbon components of the waste gas, small-molecule light hydrocarbons are unfavorable for adsorption, and large-molecule heavy hydrocarbon components cannot be desorbed and regenerated, so that long-term safe and stable operation of the catalytic combustion unit cannot be maintained.
CN102309914a discloses a method for treating malodorous waste gas discharged from a storage tank, wherein the malodorous waste gas discharged from the storage tank comprises hydrocarbons, hydrogen sulfide, organic sulfides and the like, the discharged waste gas is introduced into a waste gas treatment device, when the waste gas treatment device operates, the waste gas firstly passes through a low-temperature absorption tower, an absorbent adopts distillate oil, the distillate oil is cooled to-10-30 ℃ on a cooler, and most of hydrocarbons and most of organic sulfides are purified after the waste gas is absorbed by the distillate oil; the waste gas passing through the absorption tower enters a circulation desulfurization reactor for purification, the circulation desulfurization reactor further absorbs sulfur-containing compounds of the waste gas by using an alkali liquid absorbent, and the purified gas passing through the circulation desulfurization reactor is discharged from an exhaust barrel. The method needs to use a distillate oil system in an enterprise factory, the absorbed distillate oil needs to be regenerated, the method is only suitable for comprehensive treatment of a large-scale tank area of an oil refinery, low-temperature absorption is carried out by taking gas oil as an absorbent, and the rich absorbent returns to a process of refining in the oil refining device, so that the method is not suitable for production enterprises without related distillate oil or tank areas far away from the oil refining device.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for processing the breathing gas of a storage tank. The method combines the characteristic of unorganized discharge of the breathing gas of the storage tank, avoids the impact of the fluctuation of the breathing gas quantity and the concentration of hydrocarbon substances in the breathing gas on the catalytic oxidation, reduces the scale of the catalytic oxidation device, and ensures the long-term safe and stable operation of the catalytic oxidation unit.
According to the treatment method of the storage tank breathing gas, the storage tank breathing gas is introduced into the absorption tower, the absorbent is sprayed into the absorption tower for treatment, the treated gas enters the catalytic oxidation unit, when the storage tank does not breathe gas or the gas quantity is low, the absorption liquid is thermally regenerated by adopting high-temperature purified gas generated by the catalytic oxidation unit, and the generated hydrocarbon-containing desorption gas enters the catalytic oxidation unit for treatment, so that the safe and stable operation of the catalytic oxidation unit can be maintained.
In the invention, the gas of the storage tank mainly contains volatile hydrocarbon substances, sulfides and other pollutants, the gas displacement and the pollutant concentration of the gas vary greatly with the form, the volume, the property of storage materials and the operation parameters of the storage tank, and the concentration of non-methane total hydrocarbon is several hundred to hundreds of thousands mg/m 3 Sulfide concentration is tens to thousands mg/m 3 The respiratory gas emission is mainly concentrated in small respiration when the air temperature is increased in the morning and in large respiration when the materials are collected, so that no waste gas is emitted or the exhaust amount is tiny in the afternoon and evening due to the fact that the air temperature is reduced or the materials are not collected. The tank breathing gas mainly originates from petrochemical industry tanks, such as oil and chemical tanks, oil intermediate tanks, sewage tanks, dirty oil tanks and the like.
In the invention, the absorbent is cyclodextrin alkaline solution, the mass concentration of cyclodextrin is 1% -30%, and the mass concentration of alkali liquor is 0.1% -5%. The cyclodextrin may be at least one selected from α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin, etc., preferably γ -cyclodextrin. The alkali is at least one of strong alkali such as sodium hydroxide, potassium hydroxide and the like. The liquid-gas ratio of the absorption tower is generally 10-60L/m 3 。
In the invention, the catalytic oxidation unit mainly comprises a heat exchanger, a heater and a catalytic oxidation reactor, wherein a catalytic oxidation catalyst is arranged in the reactor, the carrier of the catalyst is a cordierite honeycomb ceramic carrier coated with alumina, the density of honeycomb holes is 200-400 meshes, active metal is Pt/Pd,the active components account for 0.1 to 2 percent of the total weight of the catalyst by element; and may contain other additives such as cerium and the like. In the catalytic oxidation unit, the inlet temperature of the reactor is 150-450 ℃, preferably 250-400 ℃, and the volume space velocity of the waste gas passing through the catalyst bed layer is 1000-50000h -1 。
In the invention, the absorption liquid mainly contains hydrocarbon substances and a small amount of sulfide pollutants. When the storage tank has no breathing gas or low gas quantity, the absorption liquid is thermally regenerated by adopting high-temperature purified gas generated by the catalytic oxidation unit, the regeneration temperature is 60-200 ℃, and the generated regenerated gas mainly contains hydrocarbon substances and enters the catalytic oxidation unit for treatment.
In the present invention, when the pH of the absorption liquid is lowered to 7 to 10, a certain amount of waste absorption liquid is discharged, and the fresh absorbent is replaced or replenished.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses cyclodextrin alkaline solution as absorbent and combines the discharge frequency of the storage tank to regulate and control, which is beneficial to the rapid absorption and desorption of hydrocarbon substances, especially when no or small discharge amount is available, hydrocarbon is released by regenerating the absorbent, thus effectively reducing the fluctuation of VOCs concentration of the respiratory gas and being beneficial to the long-term safe and stable operation of catalytic oxidation reaction.
(2) The cyclodextrin alkaline solution can adsorb sulfides and can not be desorbed at the temperature of releasing hydrocarbon substances, so that adverse effects of sulfides on subsequent catalyst oxidation are avoided, and sulfur poisoning of a catalytic oxidation catalyst is avoided.
(3) The invention utilizes catalytic oxidation purified gas to heat and regenerate the absorption liquid, the absorption liquid can be recycled after regeneration, the consumption of fresh absorbent is reduced, and the treatment cost is lower.
(4) According to the invention, pollutants such as hydrocarbon substances and sulfides are absorbed when the storage tank has the breathing gas, and the hydrocarbon substances are released into the catalytic oxidation treatment unit by heating the absorption liquid through the catalytic oxidation high-temperature purified gas when the storage tank does not have the breathing gas or the gas quantity is very low, so that the catalytic oxidation can be operated with the greatest energy self-sufficient degree, no additional heating source is needed, the scale and the operation cost of the device are reduced, and the long-term safe and stable operation of the catalytic oxidation unit is ensured.
Detailed Description
The processing method and effect of the present invention will be further described with reference to the following examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
In the invention, the non-methane total hydrocarbon is detected by adopting a gas chromatography in HJ/T38 'determination of non-methane total hydrocarbon in fixed pollution source exhaust'; the sulfide is detected by gas chromatography in GB/T14678 determination of air quality hydrogen sulfide, methyl mercaptan, methyl sulfide and the like.
Example 1
The fluctuation range of the concentration of non-methane total hydrocarbon in the breathing gas of a certain oil refinery storage tank is 5000-100000mg/m 3 Sulfide (mainly hydrogen sulfide) concentration of 50-300mg/m 3 The respiratory gas amount is 0-300 Nm 3 /h。
Firstly, the gas is introduced into an absorption tower, and gamma-cyclodextrin alkaline aqueous solution (the mass concentration of sodium hydroxide in the solution is 1% and the mass concentration of cyclodextrin is 15%) is sprayed into the absorption tower to fully contact, and part of organic matters are absorbed, so that the fluctuation range of the concentration of non-methane total hydrocarbon is reduced to 8000-30000mg/m 3 The concentration of the organic matters is homogenized, the treated gas enters a catalytic oxidation unit for deep purification, and the absorption liquid is circularly absorbed by a circulating pump. The designed liquid-gas ratio of the absorption tower is 20L/m 3 . In the catalytic oxidation unit, the inlet temperature of the reactor is 280-300 ℃, and the volume space velocity of waste gas passing through the catalyst bed layer is 10000h -1 . When the storage tank has no breathing gas or low gas quantity, the high-temperature purified gas generated by the catalytic oxidation unit is adopted to heat the absorption liquid for regeneration, the regeneration temperature is controlled to be 80-150 ℃, and the desorption gas generated by the hydrocarbon substances enters the catalytic oxidation unit for treatment, thereby avoiding high temperatureThe impact of the storage tank breathing gas with high concentration and fluctuation on the catalytic oxidation unit also reduces the energy consumption of the catalytic oxidation heat standby when no breathing gas is discharged or the gas quantity is very low, thereby maintaining the safe and stable operation of the catalytic oxidation unit. When the pH of the absorption liquid was lowered to 8, a certain amount of waste absorption liquid was discharged. In the purified gas, the removal rate of non-methane total hydrocarbon is more than 99 percent, and various pollutant indexes meet the existing emission standard.
Wherein the carrier of the hydrocarbon oxidation catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb holes is 200 meshes, the active metals are Pt and Pd, the Pt content is 0.2%, and the Pd content is 0.15%.
The device stably operates for more than 1 year, the concentration of the waste gas entering the catalytic oxidation reactor is always stabilized below 25% of the lower explosion limit through the absorption pretreatment of the absorption liquid in spite of the high concentration of the breathing gas of the storage tank, the occurrence frequency of the catalytic oxidation over-temperature interlocking stop is greatly reduced, and the catalyst poisoning or the exceeding of sulfide does not occur. The scale and the operation cost of the device can be greatly reduced, and the investment and the operation cost are reduced by more than 80 percent compared with the absorption treatment method of the invention.
Example 2
The fluctuation range of the concentration of non-methane total hydrocarbon in the breathing gas of a certain oil refinery storage tank is 2000-60000mg/m 3 Sulfide (mainly hydrogen sulfide) concentration of 100-600mg/m 3 The respiratory gas amount is 0-300 Nm 3 /h。
Firstly, the gas is introduced into an absorption tower, and gamma-cyclodextrin alkaline aqueous solution (the mass concentration of sodium hydroxide in the solution is 3% and the mass concentration of cyclodextrin is about 10%) is sprayed for full contact, and part of organic matters are absorbed, so that the fluctuation range of the concentration of non-methane total hydrocarbon is reduced to 3000-25000mg/m 3 The concentration of the organic matters is homogenized, the treated gas enters a catalytic oxidation unit for deep purification, and the absorption liquid is circularly absorbed by a circulating pump. The designed liquid-gas ratio of the absorption tower is 15L/m 3 . In the catalytic oxidation unit, the inlet temperature of the reactor is 280-300 ℃, and the volume space velocity of waste gas passing through the catalyst bed layer is 10000h -1 . Wherein the carrier of the hydrocarbon oxidation catalyst is a cordierite honeycomb carrier coated with alumina, the density of the honeycomb holes is 200 meshes, and the activity is highThe metals are Pt and Pd, the Pt content is 0.2%, and the Pd content is 0.15%. When the storage tank has no breathing gas or low gas quantity, the high-temperature purified gas generated by the catalytic oxidation unit is adopted to heat the absorption liquid for regeneration, the regeneration temperature is controlled to be 80-130 ℃, and desorption gas containing hydrocarbon substances is generated to enter the catalytic oxidation unit for treatment, so that the impact of the high-concentration and large-fluctuation storage tank breathing gas on the catalytic oxidation unit is avoided, the energy consumption of the standby of the catalytic oxidation heat when no breathing gas is discharged or the gas quantity is low is also reduced, and the safe and stable operation of the catalytic oxidation unit is maintained. When the pH of the absorption liquid was lowered to 9, a certain amount of waste absorption liquid was discharged. In the purified gas, the removal rate of non-methane total hydrocarbon is more than 99 percent, and various pollutant indexes meet the existing emission standard.
The device stably operates for more than 1 year, the safety risk that the concentration of the waste gas entering the catalytic oxidation reactor reaches the explosion range due to the fluctuation of the concentration of the breathing gas is avoided, the frequency of occurrence of catalytic oxidation over-temperature interlocking shutdown is greatly reduced, and catalyst poisoning or sulfide exceeding is avoided. The scale and the operation cost of the device can be greatly reduced, and the investment and the operation cost are reduced by more than 70 percent compared with the absorption treatment method without using the invention.
Example 3
The fluctuation range of the concentration of non-methane total hydrocarbon in the breathing gas of a certain refinery storage tank is 1000-120000mg/m 3 Sulfide (mainly hydrogen sulfide) concentration of 300-1000mg/m 3 The respiratory gas amount is 0-300 Nm 3 /h。
Firstly, the gas breathed in a storage tank enters an absorption tower, and gamma-cyclodextrin alkaline aqueous solution (the mass concentration of sodium hydroxide in the solution is 5 percent and the mass concentration of cyclodextrin is about 15 percent) is sprayed into the absorption tower to fully contact, and part of organic matters are absorbed, so that the fluctuation range of the concentration of non-methane total hydrocarbon is reduced to 3000-30000mg/m 3 The concentration of the organic matters is homogenized, the treated gas enters a catalytic oxidation unit for deep purification, and the absorption liquid is circularly absorbed by a circulating pump. The designed liquid-gas ratio of the absorption tower is 30L/m 3 . In the catalytic oxidation unit, the inlet temperature of the reactor is 280-300 ℃, and the volume space velocity of waste gas passing through the catalyst bed layer is 10000h -1 . Wherein the carrier of the hydrocarbon oxidation catalyst is cordierite coated with aluminaThe stone honeycomb carrier has a honeycomb pore density of 200 meshes, active metals of Pt and Pd, a Pt content of 0.2% and a Pd content of 0.15%. When the storage tank has no breathing gas or low gas quantity, the purified gas generated by the catalytic oxidation unit is adopted to heat the absorption liquid for regeneration, the regeneration temperature is controlled to be 80-170 ℃, and the desorption gas generated by the hydrocarbon substances enters the catalytic oxidation unit for treatment, so that the impact of the high-concentration and large-fluctuation storage tank breathing gas on the catalytic oxidation unit is avoided, the energy consumption of the standby of the catalytic oxidation heat when no breathing gas is discharged or the gas quantity is low is also reduced, and the safe and stable operation of the catalytic oxidation unit is maintained. When the pH of the absorption liquid was lowered to 10, a certain amount of waste absorption liquid was discharged. In the purified gas, the removal rate of non-methane total hydrocarbon is more than 99 percent, and various pollutant indexes meet the existing emission standard.
The device stably operates for more than 1 year, the safety risk that the concentration of the waste gas entering the catalytic oxidation reactor reaches the explosion range due to the fluctuation of the concentration of the breathing gas is avoided, the frequency of occurrence of catalytic oxidation over-temperature interlocking shutdown is greatly reduced, and catalyst poisoning or sulfide exceeding is avoided. The scale and the operation cost of the device can be greatly reduced, and the investment and the operation cost are reduced by more than 85 percent compared with the absorption treatment method without using the invention.
Example 4
The procedure is as in example 1, except that alpha-cyclodextrin is used. The designed absorption liquid-gas ratio is 40L/m 3 The mass concentration of the cyclodextrin is 15%, the occurrence frequency of the catalytic oxidation over-temperature interlocking shutdown is greatly reduced, the scale and the operation energy consumption of the device are greatly reduced, and the investment and the operation cost are reduced by more than 50% compared with those of the absorption treatment method.
Example 5
The procedure is as in example 1, except that beta-cyclodextrin is used. The designed absorption liquid-gas ratio is 50L/m 3 The mass concentration of the cyclodextrin is 3%, the occurrence frequency of the catalytic oxidation over-temperature interlocking shutdown is greatly reduced, the device scale and the operation energy consumption are reduced, and the investment and the operation cost are reduced by more than 60% compared with those of the absorption treatment method.
Comparative example 1
The procedure is as in example 1, except that a gamma cyclodextrin solution is used, without addition of base. As the respiratory gas contains sulfide, the acidity of the absorption liquid is continuously enhanced, so that the cyclodextrin is partially hydrolyzed, the concentration homogenization effect on the respiratory gas is greatly reduced, the catalytic oxidation device is subjected to over-temperature interlocking, the sulfide removal effect is limited, the catalytic oxidation catalyst is poisoned, and the exhaust gas exceeds the standard.
Comparative example 2
The procedure is as in example 1, except that lye absorption is used. Sulfide in the gas of the storage tank can be removed only, impact of organic pollutants in the gas to the catalytic oxidation unit can not be eliminated, and the catalytic oxidation unit frequently generates over-temperature interlocking stop.
Comparative example 3
The difference from example 1 is that the adsorption-desorption concentration homogenization treatment tank is performed with activated carbon to breathe gas. Because the heavy hydrocarbon component is adsorbed on the activated carbon, the heavy hydrocarbon component is not easily desorbed, the adsorption capacity of the activated carbon is quickly reduced, and the capability of coping with the fluctuation of the concentration of the breathing gas is gradually lost.
Claims (8)
1. A method of processing tank breathing gas, characterized by: introducing the gas breathed from the storage tank into an absorption tower, spraying an absorbent for treatment, and introducing the treated gas into a catalytic oxidation unit, wherein when the storage tank is free of the gas breathed, the purification gas generated by the catalytic oxidation unit is used for carrying out thermal regeneration on the absorption liquid, the regeneration temperature is 60-200 ℃, and the generated desorption gas containing hydrocarbon enters the catalytic oxidation unit for treatment, so that the safe and stable operation of the catalytic oxidation unit can be maintained; the absorbent is cyclodextrin alkaline solution, the mass concentration of cyclodextrin is 1% -30%, and the mass concentration of alkali liquor is 0.1% -5%; the catalytic oxidation unit comprises a heat exchanger, a heater and a catalytic oxidation reactor, wherein a catalytic oxidation catalyst is filled in the catalytic oxidation reactor, the carrier of the catalyst is a cordierite honeycomb ceramic carrier coated with alumina, the density of honeycomb holes is 200-400 meshes, active metal is Pt/Pd, and the active component accounts for 0.1% -2% of the total weight of the catalyst by element; the storage tank breathes gas and contains volatile hydrocarbon substances and sulfide pollutants.
2. The method according to claim 1, characterized in that: in the storage tank breathing gas, the concentration of non-methane total hydrocarbon is hundreds to hundreds of thousands mg/m 3 Sulfide concentration is tens to thousands mg/m 3 。
3. The method according to claim 1, characterized in that: the storage tank breathing gas is derived from at least one of petroleum products and chemical storage tanks of petrochemical enterprises, an oil intermediate tank, a sewage tank and a dirty oil storage tank.
4. The method according to claim 1, characterized in that: the cyclodextrin is at least one selected from alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
5. The method according to claim 1, characterized in that: the alkali is at least one of sodium hydroxide and potassium hydroxide alkali.
6. The method according to claim 1, characterized in that: the liquid-gas ratio of the absorption tower is 10-60L/m 3 。
7. The method according to claim 1, characterized in that: in the catalytic oxidation unit, the inlet temperature of the reactor is 150-450 ℃, and the volume space velocity of the waste gas passing through the catalyst bed layer is 1000-50000h -1 。
8. The method according to claim 1, characterized in that: when the pH of the absorption liquid is reduced to 7-10, a certain amount of waste absorption liquid is discharged, and the fresh absorbent is replaced or replenished.
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