CN113117496A - Method and device for treating oil refining alkaline residue acidified tail gas - Google Patents
Method and device for treating oil refining alkaline residue acidified tail gas Download PDFInfo
- Publication number
- CN113117496A CN113117496A CN201911418211.6A CN201911418211A CN113117496A CN 113117496 A CN113117496 A CN 113117496A CN 201911418211 A CN201911418211 A CN 201911418211A CN 113117496 A CN113117496 A CN 113117496A
- Authority
- CN
- China
- Prior art keywords
- desulfurization
- catalyst
- catalytic oxidation
- reactor
- unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000007670 refining Methods 0.000 title claims description 16
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 91
- 230000023556 desulfurization Effects 0.000 claims abstract description 88
- 239000003054 catalyst Substances 0.000 claims abstract description 84
- 230000003647 oxidation Effects 0.000 claims abstract description 76
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 76
- 230000003197 catalytic effect Effects 0.000 claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 61
- 239000002912 waste gas Substances 0.000 claims abstract description 49
- 230000020477 pH reduction Effects 0.000 claims abstract description 43
- 238000006900 dealkylation reaction Methods 0.000 claims abstract description 40
- 230000020335 dealkylation Effects 0.000 claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 239000011593 sulfur Substances 0.000 claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- 239000002131 composite material Substances 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 36
- 239000002699 waste material Substances 0.000 claims description 34
- 239000004215 Carbon black (E152) Substances 0.000 claims description 26
- 229930195733 hydrocarbon Natural products 0.000 claims description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 24
- 239000002808 molecular sieve Substances 0.000 claims description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 22
- 239000000919 ceramic Substances 0.000 claims description 20
- 229910052878 cordierite Inorganic materials 0.000 claims description 18
- 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 compound [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 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 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 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003518 caustics Substances 0.000 claims description 10
- 239000010802 sludge Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000006096 absorbing agent Substances 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- -1 sulfide sodium salt Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000010815 organic waste Substances 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000006255 coating slurry Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
- B01D53/75—Multi-step processes
-
- 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
-
- 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
-
- 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
- B01D53/869—Multiple step processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/08—Recovery of used refining agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- 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
-
- 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
- B01D2257/702—Hydrocarbons
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to oil refiningThe method and the device for treating the tail gas from the acidification of the alkaline residue are characterized in that the tail gas from the acidification of the alkaline residue is introduced into a catalytic oxidation desulfurization unit, the desulfurization unit mainly comprises a catalytic oxidation desulfurization module and a sulfur conversion module, and sulfides are catalytically oxidized into SO in the presence of a desulfurization catalyst2And producing a second exhaust stream; the second exhaust gas flows into a sulfur conversion module to convert SO2Conversion to SO3And generating a third waste gas flow; the third waste gas flow enters a sulfur absorption unit to absorb SO3Thereafter generating a fourth exhaust stream; and introducing the fourth waste gas stream into a catalytic oxidation dealkylation unit to remove VOCs and discharge purified gas. The method can realize efficient and stable treatment of the acidified tail gas, avoid the toxic action of sulfide in the tail gas on the catalytic oxidation catalyst, maintain the long-term stable operation of the catalytic oxidation unit, remarkably reduce the use amount of the acidifying reagent and have better economy.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a method and a device for treating oil refining alkaline residue acidified tail gas.
Background
In the process of refining oil products in an oil refinery by alkaline washing, alkaline waste liquid containing high-concentration pollutants is generated, and the emission of COD, sulfide and phenol of the alkaline waste liquid accounts for more than 40-50% of the emission of the pollutants in the oil refinery. Due to the particularity of the components of the alkaline residue waste liquid, the acidification or neutralization pretreatment is generally adopted, so that not only can petroleum acids such as sulfide and phenol be recovered, but also the difficulty of subsequent sewage treatment can be reduced, and the impact of the alkaline residue waste liquid on a sewage treatment field is avoided. However, in the process of recovering petroleum acids such as phenol by acidification, high-concentration organic waste gas containing sulfide, phenol and the like is discharged, and the treatment difficulty is high.
CN103771607A discloses a method for treating oil refining alkaline residue waste liquid by using gas and SO2The mixed gas is used for carrying out acidification treatment on the alkali residue waste liquid, the acidified tail gas is volatilized along with the continuous enhancement of acidity, and the acidification is stopped when the pH value reaches 2-7; the acidified tail gas is burnt to generate burning tail gas, and oxygen or air is needed to be supplemented to ensure sufficient burning; the incineration tail gas enters a sulfuric acid device to produce sulfuric acid; settling the acidified acidic waste liquid, and recovering an oil phase. The invention can efficiently remove sulfide in the alkaline residue waste liquid, burn the sulfide to produce sulfuric acid, effectively reduce COD and recover crude phenol. However, the acidified tail gas generated by the method needs to be matched with an incineration device and a sulfuric acid production device, and many enterprises do not have the condition for newly building the matched facility.
CN103771608A discloses a method for treating oil refining alkaline residue waste liquid by using deoxidized flue gasAcidifying the alkaline residue waste liquid, and stopping acidifying when the pH value of the waste liquid reaches 2-7; organic sulfides and H produced by acidification2S, acidifying the tail gas, and sending the tail gas to an acid gas pipe network of a refinery; settling the acidified acid waste liquid, and recovering an oil phase. The method can efficiently remove sulfides in the alkaline residue waste liquid, recover crude phenol and effectively reduce COD. However, the method needs to rely on an acid gas pipe network, and is not suitable for enterprises without the acid gas pipe network.
CN205473138U discloses a comprehensive treatment device for caustic sludge waste liquid, which comprises an acidification settling unit, an oil phase recovery unit, a tail gas treatment unit and a single-stage continuous evaporation crystallization separation unit, wherein the acidification settling unit comprises material conveying equipment, a pipeline mixer and an acidification settling tank; the oil phase recovery unit comprises an oil phase storage tank and oil phase refining equipment; the tail gas treatment unit comprises an organic amine washing tower and a diesel oil absorption tower; the single-stage continuous evaporation crystallization separation unit comprises a neutralization water adjusting tank, a single-stage continuous evaporation crystallization system and a centrifugal separator. The device can carry out high-efficient processing to high concentration sulphide and COD in the alkali sediment while, retrieves useful material in the alkali sediment waste liquid, realizes that the acidizing tail gas is up to standard and discharges. However, the adoption of organic amine absorption and diesel oil absorption devices requires depending on the existing organic amine system and diesel oil refining device in a factory, and can not realize independent treatment.
In addition, the tail gas from the acidification of the alkaline residue contains a large amount of VOCs besides organic sulfur and hydrogen sulfide, and belongs to sulfur-containing VOCs-containing organic waste gas. The purification mode of the VOCs organic waste gas comprises various modes such as adsorption, absorption, regenerative combustion and the like, wherein catalytic oxidation is a high-efficiency removal mode. However, the catalyst is susceptible to the poisoning effect of sulfur-containing organic substances under the working condition of sulfur-containing organic waste gas, so that the catalytic activity is reduced and the catalyst is inactivated. Therefore, before the sulfur-containing organic waste gas enters the catalytic reaction, the sulfur-containing organic substances need to be treated correspondingly so as to avoid the adverse effect on the oxidation of the catalyst. CN105992633 discloses a catalytic oxidation system for a gas containing hydrogen sulphide, implementing H by means of a combination of a non-noble metal catalyst and a noble metal catalyst2S, COS and CS2The oxidation of organic sulfur can be realized at the temperature of more than 320 ℃/360 ℃,however, the non-noble metal catalyst cannot realize the efficient oxidation of the organic sulfur, and needs to be combined with a noble metal catalyst, so that the cost is high. CN100532504 discloses a process for the catalytic selective oxidation of sulfur compounds, in which the sulfides in a hydrocarbon feedstock are oxidized to SO at 500 ℃ under the action of a noble metal catalyst2. In the reaction conditions mentioned in this invention, it is required to control the oxygen content to less than 0.15 and to use a noble metal catalyst which is expensive.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a device for treating oil refining alkaline residue acidification tail gas. The method can realize efficient and stable treatment of the acidified tail gas, avoid the toxic action of sulfide in the tail gas on the catalytic oxidation catalyst, maintain the long-term stable operation of the catalytic oxidation unit, remarkably reduce the use amount of the acidifying reagent and have better economy.
The technical scheme of the invention is as follows:
a method for treating oil refining alkaline residue acidification tail gas comprises the following steps:
(1) acidifying the caustic sludge to generate acidified tail gas, namely first waste gas flow;
(2) introducing the first waste gas flow into a catalytic oxidation desulfurization unit, wherein the catalytic oxidation desulfurization unit mainly comprises a catalytic oxidation desulfurization module and a sulfur conversion module, and the sulfide is catalytically oxidized into SO in the presence of a desulfurization catalyst of the catalytic oxidation desulfurization module2And producing a second exhaust stream; the catalyst used by the catalytic oxidation desulfurization unit is prepared by coating an alumina-titanium oxide composite coating on the surface of a cordierite honeycomb ceramic carrier and then soaking the cordierite honeycomb ceramic carrier in composite slurry, wherein the composite slurry is prepared by loading an active component on an SSZ-13 molecular sieve, and the active component is vanadium, cerium or/and copper;
(3) the second exhaust stream is passed to a sulfur conversion module to convert SO2Conversion to SO3And generating a third waste gas flow;
(4) the third waste gas flow enters a sulfur absorption unit and absorbs SO by concentrated sulfuric acid3And after absorption, produces a fourth exhaust stream;
(5) and introducing the fourth waste gas stream into a catalytic oxidation dealkylation unit, removing VOCs in the presence of a hydrocarbon oxidation catalyst, and discharging a purified gas.
In the invention, the oil refining alkaline residue in the step (1) is mainly from oil refining alkaline residue waste liquid, alkaline residue waste liquid containing sodium sulfide and organic sulfide sodium salt in ethylene and petrochemical industry, organic acid salt alkaline residue waste liquid and the like, and the alkaline residue waste liquid can generate sulfur-containing organic waste gas containing sulfide, phenol, petroleum hydrocarbon substances and the like, namely acidified tail gas in the acidification or neutralization treatment process.
In the invention, the step (1) of acidification treatment is to send the caustic sludge and sulfuric acid into an acidification reactor to fully contact, control the acidification pH to be 2-7, preferably 3-4, and introduce air to improve the carrying effect of sulfides and generate acidified tail gas, wherein the tail gas mainly contains organic sulfides, hydrogen sulfide, VOCs and other substances, wherein the sulfides mainly comprise hydrogen sulfide and organic sulfides, the volume concentration is 1-90%, and the concentration of non-methane total hydrocarbons is usually thousands of mg/m3To hundreds of thousands mg/m3Wherein the concentration of the phenolic substances is 1000-100000 mg/m3。
In the invention, after the acidification treatment in the step (1), more than 99% of sulfide in the alkaline residue waste liquid can be removed. The acidic waste liquid generated by acidification treatment is kept stand for layering to recover petroleum acidic substances such as phenol, naphthenic acid and the like and neutral oil, so that the COD of the alkaline residue is greatly reduced. Usually, the COD of the caustic sludge can be reduced to below 5 ten thousand mg/L from 20-30 ten thousand mg/L, and then NaOH is added for alkali precipitation regeneration, sodium sulfate is recovered, and regenerated alkali liquor is obtained for recycling.
In the invention, the catalytic oxidation desulfurization module in the step (2) mainly comprises a desulfurization reactor, a desulfurization heat exchanger, a desulfurization heater and the like, and the first waste gas flow can pass through the desulfurization heat exchanger and SO before entering the desulfurization reactor3And the third waste gas flow discharged by the converter exchanges heat, is heated by a desulfurization heater and is sent into a desulfurization reactor. The desulfurization catalyst is filled in the desulfurization reactor, and hydrogen sulfide and organic sulfide can be oxidized into SO with high selectivity2And a large amount of reaction heat is released for the sulfur conversion module. In the catalytic oxidation desulfurization module, the inlet temperature of the reactor is controlled to be 150-450 ℃, preferably 250-400 ℃, and the waste gas passes through the catalystThe volume space velocity of the bed layer is 1000-50000h-1And controlling the outlet temperature of the reactor to be not higher than 800 ℃, and preferably 450-600 ℃. After the catalytic oxidation desulfurization reaction is completed, a second waste gas stream is discharged, wherein the second waste gas stream mainly contains SO2And volatile organic compounds.
In the present invention, the desulfurization catalyst in step (2) should have the ability to simultaneously convert the organic sulfide and hydrogen sulfide into SO with high selectivity2In order to avoid the adverse effect of any sulfide on the subsequent process, which leads to the long-term stable operation of the device. The desulfurization catalyst is prepared by coating an alumina-titanium oxide composite coating on the surface of a cordierite honeycomb ceramic carrier and then soaking the cordierite honeycomb ceramic carrier in composite slurry, wherein the composite slurry is prepared by loading an active component on an SSZ-13 molecular sieve, the active component comprises vanadium, cerium or/and copper, and the composite slurry comprises, by mass of the honeycomb carrier, 1-5% of alumina, 5-8% of titanium oxide, 1-3% of the SSZ-13 molecular sieve, 0.1-0.5% of the active component by mass of vanadium pentoxide, 0.005-0.01% of cerium oxide and 0.011-0.022% of copper oxide.
In the invention, the preparation method of the desulfurization catalyst in the step (2) comprises the following steps: (a) soaking an SSZ-13 molecular sieve in an active component precursor solution in the same volume, wherein the active component is vanadium, cerium or/and copper, and drying and roasting after soaking to obtain composite powder of the SSZ-13 molecular sieve loaded with the active component; (b) preparing the composite powder into composite slurry, placing the honeycomb carrier coated with the alumina-titanium oxide composite coating into the composite slurry for dipping, and drying and roasting to obtain the monolithic catalyst.
Wherein the SSZ-13 molecular sieve in the step (a) is synthesized by a hydrothermal method, and the specific surface area is 600-700 m2Per g, pore volume of 0.25-0.3cm3(ii)/g, wherein the micropores account for more than 90%. The active component precursor solution is prepared by dissolving ammonium metavanadate in oxalic acid solution, wherein the mass ratio of ammonium metavanadate to oxalic acid is 1 (4-5), the concentration of ammonium metavanadate is 0.35-0.66mol/L, and the molar ratio of vanadium, cerium and copper in the active component is 1 (0.1-0.2) to (0.5-1). In the prepared composite, the active component is controlled to be in the composite materialAmounts of 10% to 20%, preferably 13 to 18%. After the impregnation is finished, drying at the temperature of 100-120 ℃ for 4-6 hours, and roasting at the temperature of 500-550 ℃ for 2-4 hours.
Wherein the composite slurry of step (b) comprises: the composite material comprises composite powder, an organic binder and deionized water, wherein the mass ratio of the composite powder to the organic binder to the deionized water is 15-25:1-3: 100. The organic binder is at least one of methylcellulose, hydroxypropyl methylcellulose and the like. The honeycomb carrier is a honeycomb ceramic carrier, preferably a cordierite honeycomb ceramic carrier, and the mesh number is 200-400 meshes. The method for coating the alumina-titanium oxide composite coating on the surface of the honeycomb carrier comprises the following steps: preparing dilute nitric acid with pH of 1-2, pseudo-boehmite powder, anatase titanium dioxide, an organic binder and deionized water into slurry according to a mass ratio of 50 (5-30): 25-45): 1-5): 100, then performing ball milling for 10-20h to prepare coating slurry, placing the honeycomb carrier into the coating slurry, soaking for 1-3min, drying for 4-6 h at 100-120 ℃, and roasting for 2-4 h at 500-600 ℃. The dipping time is 1-2 min. After the impregnation is finished, drying at the temperature of 100-120 ℃ for 4-6 hours, and roasting at the temperature of 500-600 ℃ for 2-4 hours.
In the invention, the sulfur conversion module in the step (3) mainly comprises SO3A converter filled with SO2Conversion to SO3Catalysts, e.g. V2O5Catalyst, etc. for removing SO from the second exhaust gas stream by means of the reaction heat discharged from the desulfurization reactor2Conversion to SO3And form a mixture mainly containing SO3And (3) a third waste gas flow.
In the present invention, the sulfur absorption unit described in the step (4) mainly comprises SO3Absorber, circulation pump, etc., SO3Concentrated sulfuric acid is used as an absorbent in the absorber, the concentration of the concentrated sulfuric acid is 96% -98.5%, and a fourth waste gas stream is discharged after absorption. If necessary, an alkali washing facility can be arranged behind the absorption tower to ensure that the acid gas meets the requirements of subsequent treatment.
In the present invention, step (4) SO3And (3) recycling the absorbent in the absorber, and discharging part of concentrated sulfuric acid to the step (1) for acidifying the caustic sludge to reduce the use amount of sulfuric acid. Depending on the change in the sulfuric acid concentration, water or concentrated sulfuric acid is appropriately supplemented.
In the present invention, step (5) isAnd the fourth waste gas flow mainly contains VOCs and is introduced into a catalytic oxidation dealkylation unit, the catalytic oxidation dealkylation unit mainly comprises a dealkylation heat exchanger, a dealkylation heater, a dealkylation reactor and the like, and a hydrocarbon oxidation catalyst is filled in the reactor. The carrier of the hydrocarbon oxidation catalyst is a cordierite honeycomb ceramic carrier coated with alumina, the density of honeycomb pores is 200-300 meshes, the active metal is Pt/Pd, and the active component accounts for 0.1-2% of the weight of the alumina coating in terms of elements; and other additives such as cerium and the like can be contained. In the catalytic oxidation dealkylation unit, the inlet temperature of the reactor is 150-450 ℃, the preferable temperature is 250-400 ℃, and the volume space velocity of the waste gas passing through the catalyst bed layer is 1000--1。
The invention also provides a treatment device for the oil refining alkali residue acidification tail gas treatment method, which mainly comprises an acidification unit, a catalytic oxidation desulfurization unit, a sulfur absorption unit and a catalytic oxidation dealkylation unit, wherein the acidification unit mainly comprises an acidification reactor; the catalytic oxidation desulfurization unit mainly comprises a catalytic oxidation desulfurization module and a sulfur conversion module, wherein the catalytic oxidation desulfurization module mainly comprises a desulfurization heat exchanger, a desulfurization heater, a desulfurization reactor and the like, and a desulfurization catalyst is filled in the desulfurization reactor; the sulfur conversion module consists essentially of SO3A converter; the sulfur absorption unit mainly comprises SO3Absorption towers, circulation pumps, etc.; the catalytic oxidation dealkylation unit mainly comprises a dealkylation heat exchanger, a dealkylation heater, a dealkylation reactor and the like, wherein the dealkylation reactor is filled with a hydrocarbon oxidation catalyst.
The desulfurization catalyst filled in the desulfurization reactor is prepared by coating an alumina-titanium oxide composite coating on the surface of a cordierite honeycomb ceramic carrier and then soaking the cordierite honeycomb ceramic carrier in composite slurry, wherein the composite slurry is prepared by loading an active component on an SSZ-13 molecular sieve, the active component comprises vanadium, cerium or/and copper, the content of the alumina is 1-5%, the content of the titanium oxide is 5-8%, the content of the SSZ-13 molecular sieve is 1-3%, the content of the active component is 0.1-0.5% by weight of vanadium pentoxide, the content of the cerium oxide is 0.005-0.01%, and the content of the copper oxide is 0.011-0.022% by weight of the honeycomb carrier.
Wherein the hydrocarbon removing reactor is filled with a hydrocarbon oxidation catalyst, the carrier of the catalyst is a cordierite honeycomb ceramic carrier coated with alumina, the density of honeycomb pores is 200-300 meshes, the active metal is Pt/Pd, and the active component accounts for 0.1-2% of the weight of the alumina coating by element; and other additives such as cerium and the like can be contained.
Compared with the prior art, the invention has the following beneficial effects:
(1) aiming at the adverse effect of the acidified tail gas on the catalytic oxidation treatment section, the inventor of the invention researches and discovers that the high-efficiency and stable treatment of the acidified tail gas of the alkali residue waste liquid can be realized by combining the desulfurization catalyst provided by the invention with the specific technological process, the toxic action of sulfide in the acidified tail gas on the catalytic oxidation catalyst can be avoided, the long-term stable operation of the catalytic oxidation unit is maintained, the consumption of sulfuric acid is reduced, and the economy is better.
(2) The desulfurization catalyst provided by the invention has good catalytic oxidation desulfurization effect in high-concentration sulfur-containing waste gas, and can realize the efficient conversion of organic sulfide into SO2And the selectivity of sulfur dioxide is high, thereby avoiding the adverse effect of sulfur-containing compounds on hydrocarbon oxidation catalysts.
(3) Because the waste gas after being treated by the desulfurization catalyst mainly contains SO2The invention can prepare high-concentration SO3The gas is used for preparing sulfuric acid and is recycled as an acidifier, so that the economy is remarkably improved; and the catalyst can not enter a subsequent hydrocarbon removal unit to influence the effect of the hydrocarbon oxidation catalyst, thereby ensuring the long-term stable operation of the catalytic oxidation unit.
Drawings
FIG. 1 is a process flow diagram of the treatment process of the present invention.
Wherein, the A-acidification reactor, the B-desulfurization heat exchanger, the C-desulfurization heater, the D-desulfurization reactor and the E-SO3Converter, F-SO3The system comprises an absorption tower, a G-dealkylation heat exchanger, an H-dealkylation heater and an I-dealkylation reactor; a-catalytic desulfurization catalyst, b-preparation of SO3Catalyst, c-hydrocarbon oxidation catalyst; 1-alkaline residue waste liquid, 2-concentrated sulfuric acid, 3-air, 4-acidified waste liquid, 5-first waste gas flow, 6-second waste gas flow, 7-third waste gas flow, 8-fourth waste gas flow, 9-concentrated sulfuric acid absorbent, 10-concentrated sulfuric acid outlet absorption tower, 11-make-up water or concentrated sulfuric acid,12-purge gas.
Detailed Description
The treatment method and effect of the present invention will be further described by examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the invention, the non-methane total hydrocarbon is detected by gas chromatography in HJ/T38 determination of non-methane total hydrocarbon in exhaust gas of fixed pollution source; detecting the sulfide by gas chromatography in GB/T14678 determination of hydrogen sulfide, methyl mercaptan, methyl sulfide and the like in air quality; phenol was detected by gas chromatography in air and exhaust gas monitoring and analysis method (fourth edition) published by the State environmental protection agency.
The device disclosed by the invention adopts the figure 1, and mainly comprises an acidification unit, a catalytic oxidation desulfurization unit, a sulfur absorption unit and a catalytic oxidation dealkylation unit, wherein the acidification unit mainly comprises an acidification reactor A, and the catalytic oxidation desulfurization unit mainly comprises a desulfurization heat exchanger B, a desulfurization heater C, a desulfurization reactor D and SO3A converter E, a catalytic desulfurization catalyst a is filled in the desulfurization reactor, and the sulfur absorption unit mainly comprises SO3Absorption tower F, filled with SO3A catalyst; the catalytic oxidation dealkylation unit mainly comprises a dealkylation heat exchanger G, a dealkylation heater H and a dealkylation reactor I, wherein a hydrocarbon oxidation catalyst c is filled in the reactor.
The invention adopts the processing method of the device shown in the attached figure 1, the caustic sludge 1 and the sulfuric acid 2 are mixed and introduced into an acidification reactor A for acidification, air 3 is introduced for stripping, the produced acidified waste liquid 4 is further treated by dephenolization after the oil phase is recovered, and then NaOH is added for alkaline precipitation and regeneration, and the sodium sulfate is recovered, so that the regenerated alkali liquor is obtained for recycling. The first waste gas stream 5 produced by acidification, mainly containing hydrogen sulphide, organic sulphides and volatile organic compounds, is subjected to a de-acidificationThe sulfur heat exchanger B and the desulfurization heater C enter a desulfurization reactor D, a catalytic desulfurization catalyst a is filled in the reactor D, and hydrogen sulfide and organic sulfide in the waste gas are catalytically oxidized into SO2To produce a gas containing mainly SO2And a second offgas stream 6 of VOCs into SO3Converter E, SO2Conversion to SO3Form a catalyst mainly containing SO3And VOCs third waste gas flow 7 enters SO after heat is recovered by a desulfurization heat exchanger B3The absorption tower F adopts concentrated sulfuric acid absorbent 9 to absorb SO3Forming a fourth waste gas flow 8 containing VOCs, discharging concentrated sulfuric acid 10 from the absorption tower, and circularly using the concentrated sulfuric acid as an absorbent, wherein part of the concentrated sulfuric acid is used as an alkaline residue acidifying reagent; supplementing water or concentrated sulfuric acid 11 according to the concentration of the concentrated sulfuric acid in the absorption tower; the fourth waste gas flow 8 enters a catalytic oxidation dealkylation unit, sequentially passes through a dealkylation heat exchanger G, a dealkylation heater H and a dealkylation reactor I, is filled with a hydrocarbon oxidation catalyst c, and oxidizes organic matters in the waste gas into CO2And H2And O, generating purified gas 12 after recovering reaction heat and discharging.
Example 1
An oil refinery adopts the flow shown in figure 1 to carry out acidification treatment on the catalytic gasoline and liquid hydrocarbon mixed caustic sludge waste liquid. The specific process is as follows:
(1) using concentrated sulfuric acid to carry out acidification treatment on the alkaline residue waste liquid, controlling the pH value of the acidified waste liquid to be 3-4 when the maximum treatment capacity of the alkaline residue is 1t/h, simultaneously introducing air into an acidification reactor, stirring and blowing off, and generating a first waste gas flow with the gas amount of 30-100Nm3The volume concentration of sulfide is 5-30%, and the total hydrocarbon of non-methane is 5000-3The concentration of volatile phenol is 3000-80000mg/m3. After the acidification treatment, more than 99 percent of sulfide in the alkaline residue waste liquid can be removed. Settling the acidified waste liquid to recover phenol and other acidic petroleum substances, performing alkali precipitation regeneration with NaOH, recovering sodium sulfate salt, and blending the obtained regenerated alkali liquid for reuse.
(2) Introducing the first waste gas flow generated by acidification into a catalytic desulfurization reaction unit, controlling the inlet temperature of a desulfurization reactor at 260-280 ℃, the outlet temperature of the reactor at 450-550 ℃, and the volume space velocity of the waste gas passing through a catalyst bed layer at 15000h-1. After the reactionTo produce SO-containing2And a second exhaust stream of VOCs.
Wherein the catalytic desulfurization catalyst filled in the desulfurization reactor is as follows: based on the mass of the honeycomb carrier, the content of the SSZ-13 molecular sieve is 1.2 percent, the content of the active component is 0.136 percent based on vanadium pentoxide, the content of copper oxide is 0.115 percent, and the content of cerium oxide is 0.025 percent; the mass of the titanium oxide accounts for 5% of that of the honeycomb carrier, and the mass of the aluminum oxide accounts for 5% of that of the honeycomb carrier. The preparation method of the catalyst comprises the following steps: (1) preparing an active component precursor solution from the active component precursor according to a molar ratio of V to Ce to Cu =1 to 0.1 to 1, wherein the concentration of ammonium metavanadate is 0.52mol/L, the concentration of copper nitrate is 0.52mol/L, and the concentration of cerium nitrate is 0.052 mol/L. Soaking an SSZ-13 molecular sieve in an active component precursor solution in the same volume, drying at 100 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain composite powder, wherein the active component accounts for 15% of the mass of the composite. (2) Preparing slurry from dilute nitric acid with the pH of 1.5, pseudo-boehmite powder, anatase titanium dioxide, methylcellulose and deionized water according to the mass ratio of 50:25:30:2:100, carrying out ball milling for 15 hours, soaking the honeycomb ceramic carrier in the coating slurry for 2 minutes, drying at 100 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the honeycomb carrier coated with the titanium oxide-aluminum oxide coating, wherein the mass of titanium oxide accounts for 5% of that of the honeycomb carrier, and the mass of aluminum oxide accounts for 5% of that of the honeycomb carrier. (3) Preparing the composite powder in the step (1) into slurry, wherein the mass ratio of the composite powder to the methylcellulose to the deionized water is 20:3:100, soaking the honeycomb carrier coated with the titanium oxide-aluminum oxide coating for 2 minutes, drying at 100 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours.
(3) The second exhaust stream enters SO3A converter to convert SO2Conversion to SO3，SO3The converter is internally provided with a V2O5A catalyst. From SO3Converter discharge, containing mainly SO3And VOCs, preheating the first waste gas flow by a desulfurization heat exchanger, recovering heat, and then introducing into SO3An absorption unit.
(4) The third waste gas flow enters SO3SO of absorption unit3An absorption tower for absorbing SO by using 98-98.5% concentrated sulfuric acid3By concentrated sulfuric acidThe pump circularly absorbs the concentrated sulfuric acid, and partial concentrated sulfuric acid is discharged from the absorption tower to be used as an acidification reagent. The concentration of the concentrated sulfuric acid in the absorption tower is adjusted by periodically supplementing water or concentrated sulfuric acid. The fourth offgas stream discharged from the absorber column contains mainly VOCs.
(5) And the fourth waste gas flow containing VOCs enters a catalytic oxidation and dealkylation unit for treatment, a reactor is filled with a hydrocarbon oxidation catalyst, the carrier of the catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb pores is 200 meshes, active metals are Pt and Pd, and the content of Pt is 0.2 percent and the content of Pd is 0.15 percent based on the weight of elements in the alumina coating. The volume space velocity of the waste gas of the catalytic oxidation dealkylation unit passing through the catalyst bed layer is not more than 12000h-1The reactor inlet temperature was 280 ℃ and 300 ℃. The concentration of non-methane total hydrocarbon in the treated waste gas is lower than 15mg/m3The concentration of sulfide is lower than 40mg/m3. The device stably operates for more than 1 year, and catalyst poisoning or standard exceeding of sulfide does not occur.
Example 2
The difference from example 1 is that: and (3) filling different catalysts in the desulfurization reactor in the step (2). The preparation process of the catalyst comprises the following steps: the same procedure as in example 1 was followed except that an active ingredient precursor solution was prepared in which the concentration of ammonium metavanadate was 0.52mol/L and the concentration of copper nitrate was 0.52mol/L at a molar ratio of V: Cu =1: 1. In the catalyst, based on the mass of the honeycomb carrier, the content of the SSZ-13 molecular sieve is 1.2%, the content of the active component is 0.136% based on vanadium pentoxide, and the content of copper oxide is 0.116%. In order to meet the treatment effect of hydrogen sulfide and organic sulfide in the first waste gas, the volume space velocity of a catalyst bed layer of the desulfurization reactor needs to be reduced to 12000h-1And the reaction temperature was increased to 280-300 ℃. The device stably operates for more than 1 year, and catalyst poisoning or standard exceeding of sulfide does not occur.
Example 3
The difference from example 1 is that: and (3) filling different catalysts in the desulfurization reactor in the step (2). The preparation process of the catalyst comprises the following steps: the same procedure as in example 1 was followed except that an active component precursor solution was prepared in which the concentration of ammonium metavanadate was 0.52mol/L and the concentration of cerium nitrate was 0.104mol/L at a molar ratio of V: Ce =1: 0.2.In the catalyst, based on the mass of the honeycomb carrier, the content of the SSZ-13 molecular sieve is 1.2%, the content of the active component is 0.136% based on vanadium pentoxide, and the content of copper oxide is 0.116%. In order to meet the treatment effect of hydrogen sulfide and organic sulfide in the first waste gas, the volume space velocity of a catalyst bed layer of a desulfurization reactor needs to be reduced to 9000h-1And the reaction temperature was increased to 300-330 ℃. The device stably operates for more than 1 year, and catalyst poisoning or standard exceeding of sulfide does not occur.
Comparative example 1
The difference from example 1 is that: and (3) replacing the SSZ-13 molecular sieve in the catalytic desulfurization catalyst in the step (2) by using an SAPO-34 molecular sieve or a ZSM-5 molecular sieve. Test results show that the catalytic oxidation desulfurization catalyst is poisoned after about one month of operation, hydrogen sulfide and organic sulfide in the first exhaust gas flow are not completely oxidized, and partial sulfide continuously enters the catalytic oxidation hydrocarbon removal unit, so that the hydrocarbon oxidation catalyst is poisoned.
Comparative example 2
The difference from example 1 is that: active components in the catalytic desulfurization catalyst in the step (2) are cerium and copper, and vanadium is not contained. Due to incomplete oxidation of hydrogen sulfide and organic sulfides in the first exhaust stream, a portion of the sulfides continue to enter the catalytic oxidative de-hydrocarbon unit, resulting in poisoning of the hydrocarbon oxidation catalyst.
Claims (19)
1. A method for treating oil refining alkaline residue acidification tail gas is characterized by comprising the following steps: (1) acidifying the caustic sludge to generate acidified tail gas, namely first waste gas flow; (2) introducing the first waste gas flow into a catalytic oxidation desulfurization unit, wherein the catalytic oxidation desulfurization unit mainly comprises a catalytic oxidation desulfurization module and a sulfur conversion module, and the sulfide is catalytically oxidized into SO in the presence of a desulfurization catalyst2And producing a second exhaust stream; the desulfurization catalyst is prepared by coating an alumina-titanium oxide composite coating on the surface of a cordierite honeycomb ceramic carrier and then soaking the cordierite honeycomb ceramic carrier in composite slurry, wherein the composite slurry is prepared by loading an active component on an SSZ-13 molecular sieve, and the active component is vanadium, cerium or/and copper; (3) the second exhaust stream is passed to a sulfur conversion module to convert SO2Conversion to SO3And generating a third waste gas flow; (4) the third waste gas flow enters a sulfur absorption unit to absorb SO3Thereafter generating a fourth exhaust stream; (5) and introducing the fourth waste gas stream into a catalytic oxidation dealkylation unit, removing VOCs in the presence of a hydrocarbon oxidation catalyst, and discharging a purified gas.
2. The method of claim 1, wherein: the oil refining alkaline residue in the step (1) mainly comes from oil refining alkaline residue waste liquid, alkaline residue waste liquid containing sodium sulfide and organic sulfide sodium salt in ethylene and petrochemical industry, and organic acid salt alkaline residue waste liquid, and the alkaline residue waste liquid can generate acidified tail gas containing sulfide, phenol and petroleum hydrocarbon substances in the acidification or neutralization treatment process.
3. The method of claim 1, wherein: and (2) the acidification treatment in the step (1) is to send the caustic sludge and sulfuric acid into an acidification reactor to be fully contacted, control the acidification pH to be 2-7, preferably 3-4, and introduce air to generate acidification tail gas, wherein the tail gas mainly contains organic sulfides, hydrogen sulfide and VOCs.
4. The method of claim 1, wherein: the catalytic oxidation desulfurization module in the step (2) mainly comprises a desulfurization reactor, a desulfurization catalyst is filled in the desulfurization reactor, the temperature of an inlet of the reactor is controlled to be 150-450 ℃, the preferred temperature is 250-400 ℃, and the volume space velocity of waste gas passing through a catalyst bed layer is 1000-50000h-1And controlling the outlet temperature of the reactor to be not higher than 800 ℃, and preferably 450-550 ℃.
5. The method of claim 1, wherein: the desulfurization catalyst in the step (2) is prepared by coating an alumina-titanium oxide composite coating on the surface of a cordierite honeycomb ceramic carrier and then soaking the cordierite honeycomb ceramic carrier in composite slurry, wherein the composite slurry is prepared by loading an active component on an SSZ-13 molecular sieve, the active component comprises vanadium, cerium or/and copper, and based on the mass of the honeycomb carrier, the content of alumina is 1-5%, the content of titanium oxide is 5-8%, the content of the SSZ-13 molecular sieve is 1-3%, the content of the active component is 0.1-0.5% by weight of vanadium pentoxide, the content of cerium oxide is 0.005-0.01%, and the content of copper oxide is 0.011-0.022%.
6. The method of claim 5, wherein: the preparation method of the desulfurization catalyst in the step (2) comprises the following steps: (a) soaking an SSZ-13 molecular sieve in an active component precursor solution in the same volume, wherein the active component is vanadium, cerium or/and copper, and drying and roasting after soaking to obtain composite powder of the SSZ-13 molecular sieve loaded with the active component; (b) preparing the composite powder into composite slurry, placing the honeycomb carrier coated with the alumina-titanium oxide composite coating into the composite slurry for dipping, and drying and roasting to obtain the monolithic catalyst.
7. The method of claim 6, wherein: the SSZ-13 molecular sieve in the step (a) is synthesized by a hydrothermal method, and the specific surface area is 600-700 m2Per g, pore volume of 0.25-0.3cm3(ii)/g, wherein the micropores account for more than 90%.
8. The method of claim 6, wherein: in the active component precursor solution in the step (a), the concentration of ammonium metavanadate is 0.35-0.66mol/L, and the molar ratio of vanadium, cerium and copper in the active component is 1 (0.1-0.2) to (0.5-1).
9. The method of claim 6, wherein: in the compound prepared in the step (a), the active component accounts for 10-20% of the mass of the compound, and preferably 13-18%.
10. The method of claim 6, wherein: the composite slurry of step (b) comprising: the composite material comprises composite powder, an organic binder and deionized water, wherein the mass ratio of the composite powder to the organic binder is 15-25:1-3: 100; the organic binder is at least one of methylcellulose, hydroxypropyl methylcellulose and the like.
11. The method of claim 6, wherein: the honeycomb carrier in the step (b) is a honeycomb ceramic carrier, preferably a cordierite honeycomb ceramic carrier, and the mesh number is 200-400.
12. The method of claim 6, wherein: the dipping time in the step (b) is 1-2 min; after the impregnation is finished, drying at the temperature of 100-120 ℃ for 4-6 hours, and roasting at the temperature of 500-600 ℃ for 2-4 hours.
13. The method of claim 1, wherein: the sulfur conversion module of step (3) mainly comprises SO3A converter filled with SO2Conversion to SO3V of2O5Catalyst for removing SO from the second exhaust gas stream by means of the heat of reaction from the desulfurization reactor2Conversion to SO3And form a mixture mainly containing SO3And (3) a third waste gas flow.
14. The method of claim 1, wherein: the sulfur absorption unit of the step (4) mainly comprises SO3Absorber, circulating pump, SO3Concentrated sulfuric acid is used as an absorbent in the absorber, the concentration of the concentrated sulfuric acid is 96% -98.5%, and a fourth waste gas stream is discharged after absorption.
15. The method of claim 14, wherein: step (4) SO3And (3) recycling the absorbent in the absorber, and discharging part of concentrated sulfuric acid to the step (1) for acidifying the caustic sludge to reduce the use amount of sulfuric acid.
16. The method of claim 1, wherein: the catalytic oxidation dealkylation unit in the step (5) mainly comprises a dealkylation heat exchanger, a dealkylation heater and a dealkylation reactor, wherein a hydrocarbon oxidation catalyst is filled in the reactor, a carrier of the hydrocarbon oxidation catalyst is a cordierite honeycomb ceramic carrier coated with alumina, the density of honeycomb pores is 200-300 meshes, active metal is Pt/Pd, and active components account for 0.1-2% of the weight of the alumina coating in terms of elements.
17. The method according to claim 1 or 16, characterized in that: in the catalytic oxidation dealkylation unit in the step (5), the inlet temperature of the reactor is 150-450 ℃, the preferable temperature is 250-400 ℃, and the volume space velocity of the waste gas passing through the catalyst bed layer is 1000--1。
18. A treatment apparatus for the treatment method according to any one of claims 1 to 17, mainly comprising an acidification unit, a catalytic oxidation desulfurization unit, a sulfur absorption unit and a catalytic oxidation dealkylation unit, wherein the acidification unit mainly comprises an acidification reactor; the catalytic oxidation desulfurization unit mainly comprises a catalytic oxidation desulfurization module and a sulfur conversion module, wherein the catalytic oxidation desulfurization module mainly comprises a desulfurization heat exchanger, a desulfurization heater and a desulfurization reactor, and a desulfurization catalyst is filled in the desulfurization reactor; the sulfur conversion module consists essentially of SO3A converter; the sulfur absorption unit mainly comprises SO3Absorption tower, circulating pump; the catalytic oxidation dealkylation unit mainly comprises a dealkylation heat exchanger, a dealkylation heater, a dealkylation reactor and the like, wherein the dealkylation reactor is filled with a hydrocarbon oxidation catalyst.
19. The processing apparatus according to claim 18, wherein: the desulfurization catalyst filled in the desulfurization reactor is prepared by coating an alumina-titanium oxide composite coating on the surface of a cordierite honeycomb ceramic carrier and then soaking the cordierite honeycomb ceramic carrier in composite slurry, wherein the composite slurry is prepared by loading an active component on an SSZ-13 molecular sieve, the active component comprises vanadium, cerium or/and copper, the content of the alumina is 1-5%, the content of the titanium oxide is 5-8%, the content of the SSZ-13 molecular sieve is 1-3%, the content of the active component is 0.1-0.5% by weight of vanadium pentoxide, the content of the cerium oxide is 0.005-0.01%, and the content of the copper oxide is 0.011-0.022% by weight of the honeycomb carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911418211.6A CN113117496B (en) | 2019-12-31 | 2019-12-31 | Method and device for treating oil refining alkaline residue acidified tail gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911418211.6A CN113117496B (en) | 2019-12-31 | 2019-12-31 | Method and device for treating oil refining alkaline residue acidified tail gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113117496A true CN113117496A (en) | 2021-07-16 |
| CN113117496B CN113117496B (en) | 2022-10-11 |
Family
ID=76769180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911418211.6A Active CN113117496B (en) | 2019-12-31 | 2019-12-31 | Method and device for treating oil refining alkaline residue acidified tail gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113117496B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870592A (en) * | 2022-01-25 | 2022-08-09 | 李海南 | Carbon dioxide treatment equipment, treatment method and treatment system based on carbon neutralization |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100252500A1 (en) * | 2007-09-11 | 2010-10-07 | Kumfer Bryan J | Treatment of spent caustic waste |
| CN101985379A (en) * | 2010-08-02 | 2011-03-16 | 惠州市奥美特环境科技有限公司 | Treatment method for high-concentration sulfur-containing caustic sludge wastewater from oil refinery |
| CN103773426A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Treatment method of liquid hydrocarbon alkaline residue waste liquid |
| CN104556464A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Oil refining alkali dreg wastewater treatment method |
| WO2017062293A1 (en) * | 2015-10-07 | 2017-04-13 | Qatar Foundation For Education, Science And Community Development | Flow battery utilizing caustic waste |
| CN108117208A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | The processing method and processing unit of a kind of alkali residue waste liquid |
-
2019
- 2019-12-31 CN CN201911418211.6A patent/CN113117496B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100252500A1 (en) * | 2007-09-11 | 2010-10-07 | Kumfer Bryan J | Treatment of spent caustic waste |
| CN101985379A (en) * | 2010-08-02 | 2011-03-16 | 惠州市奥美特环境科技有限公司 | Treatment method for high-concentration sulfur-containing caustic sludge wastewater from oil refinery |
| CN103773426A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Treatment method of liquid hydrocarbon alkaline residue waste liquid |
| CN104556464A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Oil refining alkali dreg wastewater treatment method |
| WO2017062293A1 (en) * | 2015-10-07 | 2017-04-13 | Qatar Foundation For Education, Science And Community Development | Flow battery utilizing caustic waste |
| CN108117208A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | The processing method and processing unit of a kind of alkali residue waste liquid |
Non-Patent Citations (2)
| Title |
|---|
| 彭祥燕等: "水合肼副产碱渣吸收硫酸尾气生产亚硫酸钠的工艺研究与应用", 《中国氯碱》 * |
| 钟红梅等: "碱渣吸收硫酸尾气工艺设计与研究", 《环境工程》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870592A (en) * | 2022-01-25 | 2022-08-09 | 李海南 | Carbon dioxide treatment equipment, treatment method and treatment system based on carbon neutralization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113117496B (en) | 2022-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DK1874441T3 (en) | Catalyst for the oxidation of ammonia for coal-fired public works | |
| EP3241602B1 (en) | Process for the catalytic oxidation of ammonia in power utilities | |
| CN104941423B (en) | A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method and device | |
| US9278343B2 (en) | Zeolite blend catalysts for treating exhaust gas | |
| CN102309919B (en) | Combined treatment method for waste gas containing sulfur compounds | |
| CN101314727B (en) | Desulfurization method for gasoline | |
| CN107376989B (en) | Cu-AEI molecular sieve catalyst synthesis and application | |
| CN102049181A (en) | Purification method of sulfur-containing organic waste gas | |
| CN108671967B (en) | Solvent heat green efficient regeneration method of sintering flue gas failure SCR denitration catalyst | |
| CN106714938A (en) | A process for the oxidation of hydrogen sulfide to sulfur trioxide with subsequent sulfur trioxide removal and a plant for carrying out the process | |
| CN113117496B (en) | Method and device for treating oil refining alkaline residue acidified tail gas | |
| CN109715269B (en) | Harmful gas purifying agent for adsorbing and removing nitrogen oxides in gas flow within temperature range of 60-500 DEG C | |
| CN112978893B (en) | Treatment method and system for sulfur-containing alkaline residue waste liquid | |
| CN113121033B (en) | Oil refining alkaline residue treatment method and device | |
| CA2513339C (en) | Carbon material and exhaust gas treatment apparatus | |
| CN108704474A (en) | Coke oven flue gas and Claus tail gases combined treatment process | |
| US20060178263A1 (en) | Carbon material and flue gas treatment apparatus | |
| CN113117517B (en) | Treatment method of high-concentration sulfur-containing organic waste gas | |
| CN106362744A (en) | Desulfurization and denitrification catalyst with magnesium aluminum hydrotalcite as carriers and preparing method and application thereof | |
| CN112808303B (en) | Sulfur-containing organic waste gas catalytic oxidation catalyst and preparation method thereof | |
| CN111375299B (en) | Method for treating oil refining alkaline residue acidified tail gas | |
| CN109499310A (en) | The low temperature synthesis desulfurating method of denitration of boiler smoke | |
| CN217939720U (en) | Dust removal, denitration and desulfurization equipment for industrial kiln | |
| JP2661383B2 (en) | Exhaust gas purification catalyst | |
| CN117983241A (en) | Composite carbon monoxide combustion-supporting and denitration double-effect catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231103 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |