CN111701411B - Synthetic gas desulfurizing agent and preparation method and application thereof - Google Patents
Synthetic gas desulfurizing agent and preparation method and application thereof Download PDFInfo
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- CN111701411B CN111701411B CN202010754636.0A CN202010754636A CN111701411B CN 111701411 B CN111701411 B CN 111701411B CN 202010754636 A CN202010754636 A CN 202010754636A CN 111701411 B CN111701411 B CN 111701411B
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- metal oxide
- synthesis gas
- oxide
- desulfurizer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003009 desulfurizing effect Effects 0.000 title claims description 28
- 239000007789 gas Substances 0.000 claims abstract description 172
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 56
- 230000023556 desulfurization Effects 0.000 claims abstract description 56
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 46
- 239000011787 zinc oxide Substances 0.000 claims abstract description 40
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 116
- 238000003786 synthesis reaction Methods 0.000 claims description 116
- 239000003795 chemical substances by application Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 16
- 238000009718 spray deposition Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 11
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 7
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 7
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 4
- 150000002823 nitrates Chemical group 0.000 claims 4
- 238000002156 mixing Methods 0.000 claims 3
- 238000007493 shaping process Methods 0.000 claims 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 25
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 19
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 15
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 22
- 229910052717 sulfur Inorganic materials 0.000 description 22
- 239000011593 sulfur Substances 0.000 description 22
- 230000008929 regeneration Effects 0.000 description 20
- 238000011069 regeneration method Methods 0.000 description 20
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001694 spray drying Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 150000004763 sulfides Chemical class 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000011143 downstream manufacturing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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
- B01D53/46—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
- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/30—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses with moving purifying masses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
-
- 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
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- 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
- B01D2257/308—Carbonoxysulfide COS
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a synthetic gas desulfurizer and a preparation method and application thereof, the synthetic gas desulfurizer of the invention modifies the conventional zinc oxide desulfurizer by metal oxide and nonmetal oxide, the prepared desulfurizer has good structural stability, and still has higher capability of removing sulfides under the conditions of high water vapor partial pressure and high temperature oxidation, the synthetic gas desulfurizer is a reproducible synthetic gas solid desulfurizer for removing hydrogen sulfide and organic sulfur, which is suitable for the fluidized bed high temperature desulfurization process, and can remove hydrogen sulfide and organic sulfur in the synthetic gas, save energy and reduce consumption.
Description
Technical Field
The invention relates to the technical field of synthetic gas desulfurizing agents, and particularly relates to a synthetic gas desulfurizing agent and a preparation method and application thereof.
Background
The synthesis gas (containing fuel gas) prepared by coal gasification is the basis of novel coal chemical industry, is mainly used for synthesizing ammonia in the prior art, is mainly used for producing methanol, glycol, natural gas, special oil products and the like at present, and is also used for synthesizing fine chemicals.
The sulfur-containing compounds in the synthesis gas not only can cause corrosion of production equipment and pipelines and influence production safety, but also can cause poisoning and inactivation on the catalyst of subsequent chemical reaction and directly influence the yield and quality of the final product. The sulfur-containing compounds in the synthesis gas are removed, so that the safety production can be improved, the subsequent reaction efficiency can be guaranteed, and important sulfur resources can be recovered from the sulfur-containing compounds.
The synthesis gas desulfurization mainly comprises two modes of wet desulfurization and dry desulfurization. The wet desulfurization has three processes of chemical absorption, physical absorption and physical and chemical absorption, and has the advantages that the synthesis gas desulfurizer can be continuously circulated for desulfurization and regeneration, is suitable for large-scale production, and can recover sulfur. The wet desulphurization has the defects that the wet desulphurization is generally used in the normal-temperature and low-temperature desulphurization process, the operation energy consumption is overhigh for high-temperature synthesis gas, and the desulphurization precision is low. The dry desulfurization includes adsorption reaction methods such as zinc oxide, iron oxide, manganese oxide and active carbon, and especially the zinc oxide desulfurization is the most extensive. Dry desulfurization has many advantages of both inorganic sulfur removal and organic sulfur removal, both high temperature desulfurization and low temperature desulfurization, and high desulfurization accuracy, but dry desulfurization syngas desulfurization agents cannot be regenerated, can only be periodically operated, and are not suitable for removing a large amount of sulfides.
The sulfur-containing compounds in the coal synthesis gas contain a small amount of organic sulfur compounds such as carbonyl sulfide and carbon disulfide besides hydrogen sulfide with high concentration. The zinc oxide-based synthetic gas desulfurizer has high removal rate for removing hydrogen sulfide and can meet the requirements of downstream processes, but the zinc oxide-based synthetic gas desulfurizer has low removal rate for removing organic sulfur and can not meet the requirements of downstream processes. In order to solve the problem of low organic sulfur removal rate in the dry desulfurization of synthesis gas, the process of adding synthesis gas hydrogenation to convert organic sulfur into hydrogen sulfide before the synthesis gas zinc oxide is generally adopted at present, so that the aim of fine desulfurization of the synthesis gas is achieved by virtue of zinc oxide desulfurization. But the synthesis gas hydrogenation procedure is arranged, so that the investment cost and the operation cost are correspondingly increased, and the production control difficulty is also improved.
Therefore, the development of the synthesis gas desulfurizer for the dry method, which can continuously carry out reaction regeneration, can remove hydrogen sulfide and organic sulfur in the synthesis gas, and can save energy and reduce consumption, is an urgent problem to be solved for the desulfurization of the synthesis gas.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a synthesis gas desulfurizer as well as a preparation method and application thereof.
The invention is realized by the following steps:
the embodiment of the invention provides a synthetic gas desulfurizer which comprises the following active components in percentage by mass:
40-80% of metal oxide A, 3-10% of metal oxide B, 10-15% of metal oxide C and 1-3% of non-metal oxide D;
the metal oxide A is zinc oxide;
the metal oxide B is at least one selected from copper oxide and gallium oxide;
the metal oxide C is at least two selected from nickel oxide, cobalt oxide and molybdenum oxide;
the non-metal oxide D is at least one selected from phosphorus pentoxide and boron trioxide.
The invention also provides a preparation method of the synthetic gas desulfurizer, which comprises the following steps:
and (3) forming and roasting the slurry containing the precursors of the components to obtain the synthesis gas desulfurizer.
The invention also provides an application of the synthetic gas desulfurizer in a fluidized bed desulfurization process.
The invention has the following beneficial effects:
the invention provides a synthetic gas desulfurizer and a preparation method and application thereof, wherein the synthetic gas desulfurizer in the invention is prepared by modifying a conventional zinc oxide desulfurizer through metal oxides and nonmetal oxides, so that the prepared desulfurizer has good structural stability, still has high sulfide removal capability under the conditions of high water vapor partial pressure and high-temperature oxidation, and can remove hydrogen sulfide and organic sulfur in synthetic gas, save energy and reduce consumption.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention aims to solve the problems that the existing zinc oxide synthesis gas desulfurizer can not be repeatedly regenerated and reused; secondly, the existing zinc oxide synthesis gas desulfurizer has low organic sulfur removal rate and can not meet the requirements of downstream processes; thirdly, the physical state of the existing zinc oxide synthetic gas desulfurizer is not suitable for the fluidized bed process of the desulfurization regeneration cycle of the synthetic gas desulfurizer. Therefore, the synthesis gas desulfurizing agent which is suitable for the fluidized bed desulfurization process and can regeneratively remove the hydrogen sulfide and the organic sulfur in the synthesis gas and the preparation method thereof are provided.
In a first aspect, an embodiment of the present invention provides a syngas desulfurizing agent, which includes, by mass:
40-80% of metal oxide A, 3-10% of metal oxide B, 10-15% of metal oxide C and 1-3% of non-metal oxide D;
the metal oxide A is zinc oxide;
the metal oxide B is at least one selected from copper oxide and gallium oxide;
the metal oxide C is at least two selected from nickel oxide, cobalt oxide and molybdenum oxide;
the non-metal oxide D is at least one selected from phosphorus pentoxide and boron trioxide.
As a preferred embodiment, the syngas desulfurization agent further comprises a carrier and a binder;
preferably, the carrier and the adhesive account for 15 to 40 percent of the mass percent of the synthetic gas desulfurizer;
preferably, the support comprises at least one of pseudoboehmite and hydrated titanium dioxide powder;
preferably, the binder includes at least one of an aluminum sol and a silica sol.
Therefore, the active component in the syngas desulfurizer provided by the embodiment of the invention mainly comprises zinc oxide, and also comprises two or three of copper oxide and/or gallium oxide, nickel oxide and/or cobalt oxide and/or molybdenum oxide, phosphorus pentoxide and/or boron trioxide. And adding the active components into uniform slurry formed by a carrier and an adhesive, and performing spray forming, drying and roasting to obtain the target synthesis gas desulfurizer. Specifically, the method comprises the following steps:
(1) the main active component zinc oxide of the synthetic gas desulfurizer is from nanometer basic zinc carbonate, nanometer zinc oxide, zinc nitrate, zinc chloride and the like, preferably nanometer basic zinc carbonate and nanometer zinc oxide, and most preferably nanometer basic zinc carbonate. The content of zinc oxide in the synthetic gas desulfurizer is 40-70%, and preferably 60-70%.
(2) The active components of the synthesis gas desulfurizer, namely copper oxide and/or gallium oxide, are respectively from nitrate and/or chloride, preferably nitrate. The content of copper oxide and/or gallium oxide in the synthesis gas desulfurizer is 3-10%, preferably 5-8%.
(3) The hydrogenation active component of the synthesis gas desulfurizer is nickel oxide and/or cobalt oxide and/or molybdenum oxide which are respectively from nickel nitrate and/or cobalt nitrate and/or ammonium molybdate. The content of nickel oxide and/or cobalt oxide and/or molybdenum oxide in the synthesis gas desulfurizer is 10-15%, and preferably 11-13%.
(4) The active component phosphorus pentoxide of the synthesis gas desulfurizer is from phosphoric acid and/or ammonium phosphate and/or ammonium hydrogen phosphate and/or ammonium dihydrogen phosphate and the like; the active component of the synthesis gas desulfurizer, namely the diboron trioxide, is derived from boric acid. The content of phosphorus pentoxide and/or boron trioxide in the synthesis gas desulfurizer is 1-3%, preferably 1-2%.
(5) The synthesis gas desulfurizing agent component is from pseudo-boehmite, aluminum sol and/or silica sol and/or hydrated titanium dioxide powder. The content of alumina and/or silica and/or titania in the synthesis gas desulfurizing agent is 15-45%, preferably 15-35%.
The basic principle of desulfurization by using the synthesis gas desulfurizing agent is as follows:
in general, hydrogen sulfide in the synthesis gas can be removed by using a zinc oxide synthesis gas desulfurizing agent, and the reaction equation is shown as formula (1):
H2S+ZnO→ZnS+H2O (1)
however, the conventional zinc oxide synthesis gas desulfurizer can only be used once and cannot be regenerated circularly. According to the synthesis gas desulfurizer provided by the embodiment of the invention, the conventional zinc oxide synthesis gas desulfurizer is modified by metal oxide and nonmetal oxide, so that the synthesis gas desulfurizer has good structural stability, and still has high capability of removing hydrogen sulfide under the conditions of high water vapor partial pressure and high-temperature oxidation.
The synthesis gas desulfurizer which generates zinc sulfide in the desulfurization reactor is deactivated and then transferred to the regenerator, the zinc sulfide is converted into zinc oxide by air combustion and then returned to the desulfurization reactor for desulfurization, the reaction in the regenerator is shown as a formula (2), meanwhile, the hydrogenation active component used for modifying the synthesis gas desulfurizer also forms metal oxide in the regeneration process, and the reaction is shown as a formula (3) (M represents the hydrogenation metal active component).
2ZnS+3O2→2ZnO+2SO2 (2)
M+O2→MOx (3)
The synthesis gas desulfurizing agent with hydrogenation activity component forms metal oxide in the regeneration process so as to weaken the hydrogenation activity, so that the regenerated synthesis gas desulfurizing agent needs to reduce the metal oxide into metal with hydrogenation activity by hydrogenation, and the reaction equation is shown as (4):
MOx+H2→M+H2O (4)
the sulfur-containing compounds in the syngas are primarily hydrogen sulfide, but also contain small amounts of organic sulfides such as carbonyl sulfide, carbon disulfide, and the like. The reaction activity of the organic sulfide and the zinc oxide type synthetic gas desulfurizer is low, the removal rate is low, and the requirements of subsequent processes cannot be met. It is therefore necessary to convert the organic sulphides to hydrogen sulphide in order to ensure an effective removal of the sulphides from the synthesis gas.
Under a certain temperature and pressure, the catalyst containing hydrogenation active metal converts organic sulfide in the synthesis gas into hydrogen sulfide so as to be removed by utilizing a zinc oxide synthesis gas desulfurizer, and the reaction of converting the organic sulfide into the hydrogen sulfide is shown as formulas (5) and (6):
COS+H2→CO+H2S (5)
CS2+2H2→C+2H2S (6)
in a second aspect, an embodiment of the present invention provides a preparation method of the above syngas desulfurizing agent, including the following steps: and (3) forming and roasting the slurry containing the precursors of the components to obtain the synthesis gas desulfurizer.
The preparation method of the synthesis gas desulfurizer comprises the following specific steps:
adding a certain amount of deionized water into the alumina sol or the silica sol, slowly adding pseudo-boehmite and/or hydrated titanium dioxide powder, stirring and homogenizing for 6-10 hours to obtain slurry, continuously adding metered phosphoric acid and/or ammonium phosphate and/or ammonium hydrogen phosphate and/or ammonium dihydrogen phosphate and/or boric acid, copper oxide and/or nitrate and/or chloride of gallium, nano basic zinc carbonate and/or nano zinc oxide and/or zinc nitrate and/or zinc chloride and the like into the slurry in sequence, stirring and homogenizing the whole slurry for 6-10 hours, wherein the solid content of the slurry is 20-40%;
spray drying and forming all the slurry, controlling the temperature of a spray drying furnace chamber to be 350-450 ℃, the temperature of an outlet of a drying tower to be 150-250 ℃ and the spray pressure of the drying tower to be 2.5-4.5 MPa. Drying the spray-formed material at the temperature of 120-150 ℃ for 5-10 hours, and then roasting at the temperature of 520-650 ℃ for 4-8 hours to obtain a microspherical synthesis gas desulfurizer semi-finished product;
adding two or three of nickel nitrate, cobalt nitrate and ammonium molybdate into deionized water at room temperature to prepare a solution, soaking the synthesis gas desulfurizer semi-product in the solution at the temperature of 30-60 ℃ for 3-10 hours, filtering, drying at the temperature of 80-140 ℃ for 4-8 hours, and finally roasting at the temperature of 450-650 ℃ for 5-10 hours to obtain the finished synthesis gas desulfurizer.
Therefore, the synthesis gas desulfurizer provided by the embodiment of the invention has the following advantages:
(1) the zinc oxide based synthetic gas desulfurizer has high desulfurization precision, and especially has high desulfurization activity and large sulfur capacity of nanometer basic zinc carbonate and nanometer zinc oxide.
(2) The zinc oxide-based synthetic gas desulfurizer can completely convert organic sulfides in the synthetic gas into hydrogen sulfide through modification treatment of metal oxides such as nickel oxide and/or cobalt oxide and/or molybdenum oxide, so that the desulfurization efficiency of the synthetic gas desulfurizer is improved.
(3) The zinc oxide-based synthetic gas desulfurizer is subjected to modification treatment by metal oxides such as copper oxide and/or gallium oxide, and the activity attenuation of the synthetic gas desulfurizer is not obvious after the synthetic gas desulfurizer is regenerated for many times.
(4) The synthesis gas desulfurizer containing phosphorus pentoxide and/or diboron trioxide, which is prepared by modifying the zinc oxide-based synthesis gas desulfurizer by phosphoric acid and/or ammonium phosphate and/or ammonium hydrogen phosphate and/or ammonium dihydrogen phosphate and/or boric acid, is particularly suitable for the synthesis gas desulfurization process and the oxidation regeneration process with high water vapor content so as to maintain the desulfurization activity and the desulfurization stability of the synthesis gas desulfurizer.
(5) The synthesis gas desulfurizer using alumina and/or silica and/or titanium dioxide as the carrier has strong wear resistance, large specific surface area and pore volume, and is particularly suitable for the working conditions of fluidized bed adsorption desulfurization and regeneration.
(6) The zinc oxide-based microsphere synthetic gas desulfurizer prepared by the spray drying and forming technology is particularly suitable for the working conditions of fluidized bed desulfurization and regeneration.
The desulfurizing agent for the synthesis gas prepared by the technology has high desulfurization precision and can be used for desulfurizing the synthesis gas H2The concentration of S (containing organic sulfide) is reduced to 1.0mg/m3(ii) a The sulfur capacity of the synthetic gas desulfurizer is as high as 15-25 g (sulfur)/100 g (synthetic gas desulfurizer); the desulfurization activity of the synthetic gas desulfurizer is maintained by more than 80 percent after 50 times of regeneration; the synthetic gas desulfurizer has strong wear resistance in the adsorption regeneration cycle process, and the wear index is not lower than 3.0%.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Collecting 1058g of alumina sol (Al)2O3Content 21%), 27g of ammonium dihydrogen phosphate, 94g of copper nitrate and 1500g of basic zinc carbonate were slowly added, followed by stirring for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthesis gas desulfurizer E01.
190g of nickel nitrate and 207g of cobalt nitrate are dissolved in 600ml of water, the solution is used for soaking the synthesis gas desulfurizer E016 hours at the temperature of 50 ℃, then the synthesis gas desulfurizer E001 is obtained after drying for 4 hours at the temperature of 110 ℃ and finally roasting for 5 hours at the temperature of 500 ℃.
The desulfurizing agent E001 of the synthesis gas is at normal pressure, temperature of 400 ℃ and space velocity of 2000h－1Reducing the obtained product by using hydrogen for 60 minutes under the condition of (1) to obtain the finished product of the synthetic gas desulfurizer E1.
Example 2
Taking 1184g of aluminum sol (Al)2O3Content 21%), 27g of ammonium dihydrogen phosphate, 80g of copper nitrate and 1500g of basic zinc carbonate were slowly added, followed by stirring for 5.0 hours. At furnace temperature 40Spray drying and forming under the conditions of 0 ℃, outlet temperature of 200 ℃ and spraying pressure of 4.0 MPa. Drying the formed adsorbent at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthetic gas desulfurizer E02.
138g of nickel nitrate, 41g of ammonium paramolybdate and 132g of cobalt nitrate are dissolved in 600ml of water, the solution is used for soaking a synthesis gas desulfurizer E026 h at the temperature of 50 ℃, then the synthesis gas desulfurizer E002 is dried for 4 h at the temperature of 110 ℃, and finally the synthesis gas desulfurizer E002 is obtained by roasting for 5 h at the temperature of 500 ℃.
The desulfurizing agent E002 of the synthesis gas is at normal pressure, temperature of 400 ℃ and space velocity of 2000h－1Reducing the obtained product by using hydrogen for 60 minutes under the condition of (1) to obtain the finished product of the synthetic gas desulfurizer E2.
Comparative example 1
Collecting 1190g of aluminum sol (Al)2O3Content 21%), 120g of hydrated titanium dioxide powder was slowly added with stirring, 1350g of basic zinc carbonate was slowly added with stirring after 2.0 hours of stirring, and then further stirred for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthesis gas desulfurizer A1.
Comparative example 2
1250g of silica Sol (SiO)2Content 16%), 180g of hydrated titanium dioxide powder was slowly added with stirring, 650g of nano zinc oxide was slowly added with stirring after 2.0 hours of stirring, and then further stirred for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthesis gas desulfurizer A2.
Comparative example 3
Taking 950g of alumina sol (Al)2O3Content 21%), 180g of hydrated titanium dioxide powder was slowly added with stirring, after 2.0 hours of stirring, 1800g of basic zinc carbonate and 236g of copper nitrate were slowly added with stirring, and then further stirring was carried out for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain synthesis gas desulfurizationAnd a sulfur agent B1.
Comparative example 4
Taking 950g of alumina sol (Al)2O3Content 21%), 180g of hydrated titanium dioxide powder was slowly added with stirring, 1800g of basic zinc carbonate and 297g of gallium nitrate were slowly added with stirring after 2.0 hours of stirring, and then, stirring was further carried out for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthesis gas desulfurizer B2.
Comparative example 5
Taking 950g of alumina sol (Al)2O3Content 21%), 156g of hydrated titanium dioxide powder was slowly added with stirring, and after stirring for 2.0 hours, 32g of ammonium dihydrogen phosphate, 236g of copper nitrate and 1700g of basic zinc carbonate were slowly added with stirring, followed by further stirring for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthesis gas desulfurizer C1.
Comparative example 6
Taking 950g of alumina sol (Al)2O3Content 21%), while stirring, silica sol 813g (SiO2 content 16%) was slowly added, and after stirring for 2.0 hours, boric acid 36g, gallium nitrate 297g, and basic zinc carbonate 1700g were slowly added, followed by further stirring for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthesis gas desulfurizer C2.
Comparative example 7
807g of alumina sol (Al) was taken2O3Content 21%), 82g of hydrated titanium dioxide powder was slowly added with stirring, after 2.0 hours of stirring, 27g of ammonium dihydrogen phosphate, 100g of copper nitrate and 1700g of basic zinc carbonate were slowly added with stirring, and further stirred for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthesis gas desulfurizer D01.
196g of nickel nitrate and 86g of ammonium paramolybdate are dissolved in 600ml of water, the solution is used for soaking a synthesis gas desulfurizer D016 h at the temperature of 50 ℃, then the synthesis gas desulfurizer D1 is dried for 4 h at the temperature of 110 ℃, and finally the synthesis gas desulfurizer D1 is obtained by roasting at the temperature of 500 ℃ for 5 h.
Comparative example 8
Taking 726g of alumina sol (Al)2O3Content 21%), 82g of titanium dioxide powder was slowly added with stirring, 27g of ammonium dihydrogen phosphate, 100g of copper nitrate and 1700g of basic zinc carbonate were slowly added with stirring after 2.0 hours of stirring, and then the mixture was stirred for 5.0 hours. Spray drying and forming under the conditions of the hearth temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0 MPa. Drying the formed synthesis gas desulfurizer at 150 ℃ for 5.0 hours, and roasting at 600 ℃ for 5.0 hours to obtain the synthesis gas desulfurizer D02.
196g of nickel nitrate, 86g of ammonium paramolybdate and 20g of cobalt nitrate are dissolved in 600ml of water, the solution is used for soaking a synthesis gas desulfurizer D026 h at the temperature of 50 ℃, then the synthesis gas desulfurizer D2 is obtained after drying for 4 h at the temperature of 110 ℃ and finally roasting for 5 h at the temperature of 500 ℃.
H removal of synthesis gas desulfurizer2S evaluation method
(1) Evaluating a synthetic gas desulfurizer by using a fixed bed test device, wherein the filling amount of the synthetic gas desulfurizer is 5.0 g;
(2) the raw material gas for evaluation contains H2S2000mg/m3The water vapor content is 30 percent, and the balance is nitrogen;
(3) the evaluation conditions are normal pressure, temperature of 300 ℃ and gas space velocity of 2000h－1The total sulfur content of purified gas is more than 1mg/m3When the synthesis gas desulfurizer is considered to be penetrated and deactivated, the deactivated synthesis gas desulfurizer is regenerated by air at the temperature of 550 ℃ under normal pressure.
The evaluation of the physical properties of the desulfurizing agent for synthesis gas provided in examples and comparative examples of the present invention is shown in Table 1.
TABLE 1 physical Properties of desulfurizing Agents for Synthesis gas
As can be seen from Table 1, the synthesis gas desulfurization agent obtained by the method provided by the embodiment of the invention has higher specific surface area and pore volume and better wear resistance than the synthesis gas desulfurization agent provided by the comparative example.
Evaluation of desulfurization and regeneration performance for the syngas desulfurization agent provided in examples of the present invention and comparative examples is shown in table 2.
TABLE 2 desulfurization and regeneration Performance of syngas desulfurization agent
Note: the sulfur capacity means that the total sulfur content of the purified gas is more than 1mg/m3Mass number (g) of sulfur on 100g of the syngas desulfurization agent upon breakthrough deactivation of the syngas desulfurization agent.
As can be seen from Table 2, the synthesis gas desulfurizing agent obtained by the method provided by the embodiment of the invention can be used for synthesizing the synthesis gas H2The S concentration is reduced to 1.0mg/m3(ii) a The sulfur capacity of the synthetic gas desulfurizer reaches up to 13.3-20.1 g (sulfur)/100 g (synthetic gas desulfurizer); the desulfurization activity of the synthetic gas desulfurizer is maintained by more than 80 percent after 50 times of regeneration; the synthetic gas desulfurizer has strong wear resistance in the adsorption regeneration cycle process, and the wear index is lower than 3.0%.
Although the fresh synthesis gas desulfurizer prepared in the comparative examples 1 to 8 has higher sulfur capacity, the activity of the synthesis gas desulfurizer is greatly reduced after 50 times of regeneration, and the activity of the synthesis gas desulfurizer subjected to metal modification and nonmetal modification is reduced little after 50 times of regeneration, which shows that the zinc oxide synthesis gas desulfurizer has good regeneration performance after metal modification and nonmetal modification, and the synthesis gas desulfurizer can be subjected to multiple reaction regeneration cycles.
H removal of synthesis gas desulfurizer2Method for evaluating S and organic sulfur
(1) Evaluating a synthetic gas desulfurizer by using a fixed bed test device, wherein the filling amount of the synthetic gas desulfurizer is 5.0 g;
(2) the raw material gas for evaluation contains H2S1800mg/m3、COS200mg/m3The water vapor content is 30 percent, and the balance is nitrogen;
(3) the evaluation conditions are normal pressure, temperature of 300 ℃ and gas space velocity of 2000h－1Purifying the gas H2S content greater than 1mg/m3The syngas desulfurization agent is believed to be breakthrough deactivation.
Evaluation of desulfurization and regeneration properties for the syngas desulfurization agents provided in examples of the present invention and comparative examples is shown in table 3.
TABLE 3 desulfurization and regeneration Performance of syngas desulfurization agent
Note: the sulfur capacity means that the total sulfur content of the purified gas is more than 1mg/m3Mass number (g) of sulfur on 100g of the syngas desulfurization agent upon breakthrough deactivation of the syngas desulfurization agent.
As can be seen from Table 3, the synthesis gas desulfurizing agent obtained by the method of the invention can efficiently remove H2S, but the ability to remove organic sulfur (COS) is particularly different. The synthetic gas desulfurizing agents D1 and D2 with hydrogenation active components have better capability of removing organic sulfur (COS), and the synthetic gas desulfurizing agents E1 and E2 with hydrogenation active components after hydrogenation reduction can not only completely remove hydrogen sulfide, but also completely remove organic sulfur (COS). Shows that the conventional synthesis gas desulfurizer can remove H by adding a hydrogenation active component and reducing with hydrogen2S, and also has the function of removing organic sulfur (COS).
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The preparation method of the synthesis gas desulfurizer is characterized by comprising the following steps of carrying out spray forming and roasting treatment on slurry of precursors containing various components of the synthesis gas desulfurizer, wherein the active ingredients of the synthesis gas desulfurizer comprise the following components in percentage by mass:
40-80% of metal oxide A, 3-10% of metal oxide B, 10-15% of metal oxide C and 1-3% of non-metal oxide D;
the metal oxide A is zinc oxide;
the metal oxide B is at least one selected from copper oxide and gallium oxide;
the metal oxide C is at least two selected from nickel oxide, cobalt oxide and molybdenum oxide;
the non-metal oxide D is at least one selected from phosphorus pentoxide and boron trioxide;
the synthesis gas desulfurizer also comprises a carrier and a binder; the carrier and the binder account for 15-40% of the synthesis gas desulfurizer by mass; the carrier comprises at least one of pseudo-boehmite and hydrated titanium dioxide powder; the binder comprises at least one of an aluminum sol and a silica sol;
then at normal pressure, 400 ℃ and 2000h of space velocity-1Reducing for 60 minutes by hydrogen under the condition of (1) to obtain the finished product of the synthetic gas desulfurizer.
2. The method for preparing a syngas desulfurization agent according to claim 1, wherein the zinc oxide is obtained by decomposition of a zinc oxide precursor, and the zinc oxide precursor comprises at least one of nano basic zinc carbonate, nano zinc oxide, zinc nitrate and zinc chloride.
3. The method for preparing a desulfurizing agent for synthesis gas according to claim 2, wherein the precursor of zinc oxide is nano basic zinc carbonate.
4. The method according to claim 1, wherein the metal oxide B is obtained by decomposing a precursor of the metal oxide B, and the precursor of the metal oxide B is selected from nitrates and/or chlorides corresponding to the metals in the metal oxide.
5. The method according to claim 4, wherein the precursor of the metal oxide B is selected from nitrates corresponding to metals in the metal oxide.
6. The method according to claim 1, wherein the metal oxide C is obtained by decomposing a precursor of the metal oxide C, and the precursor of the metal oxide C is selected from nitrates and/or molybdates corresponding to the metals in the metal oxide.
7. The method according to claim 6, wherein the precursor of the metal oxide C is selected from nitrates corresponding to metals in the metal oxide.
8. The method for preparing a synthesis gas desulfurization agent according to claim 1, wherein the non-metal oxide D is obtained by decomposing a precursor of the non-metal oxide D, and the precursor of phosphorus pentoxide comprises at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate;
the diboron trioxide is obtained by decomposing a precursor of the diboron trioxide, and the precursor of the diboron trioxide is selected from boric acid.
9. The method according to claim 1, wherein the slurry is mainly obtained by mixing a binder, a carrier, precursors of each active component and water.
10. The preparation method of a desulfurizing agent for synthesis gas according to claim 9, wherein the specific preparation method of the slurry comprises the following steps:
dissolving the binder in water, stirring and mixing the binder and the carrier uniformly, and then continuously adding the precursor of the active component, mixing and stirring to obtain slurry.
11. The method of claim 1, wherein the shaping is spray shaping.
12. The method for preparing a desulfurizing agent for synthesis gas according to claim 11, wherein the temperature of the furnace chamber is 350-450 ℃, the temperature of the outlet of the drying tower is 150-250 ℃, and the spraying pressure of the drying tower is 2.5-4.5MPa in the spray forming process.
13. The method for preparing a desulfurizing agent for synthesis gas according to claim 12, further comprising drying the spray-molded material at 120-150 ℃ for 5-10 h.
14. The method for preparing desulfurizing agent for synthesis gas according to claim 13, wherein the temperature of the calcination treatment after the spray forming is 520-650 ℃ and the time is 4-8 h.
15. Use of a syngas desulfurization agent prepared according to the preparation method of any one of claims 1-14 in a fluidized bed desulfurization process.
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| CN107335445A (en) * | 2017-08-17 | 2017-11-10 | 江苏天东新材料科技有限公司 | A kind of preparation method and application of double-function fine desulfurizing agent |
| CN108940248A (en) * | 2018-06-28 | 2018-12-07 | 西南化工研究设计院有限公司 | A kind of organic sulfur hydroconversion catalyst and its preparation method and application |
| CN110586028A (en) * | 2019-10-08 | 2019-12-20 | 中国石油化工股份有限公司 | Desulfurizing agent and preparation method and application thereof |
| CN110804468A (en) * | 2019-11-27 | 2020-02-18 | 浙江天禄环境科技有限公司 | Dry desulfurization process for synthesis gas |
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