CN112547111B - Ruthenium catalyst for removing trace sulfide in benzene - Google Patents
Ruthenium catalyst for removing trace sulfide in benzene Download PDFInfo
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- CN112547111B CN112547111B CN202011620025.3A CN202011620025A CN112547111B CN 112547111 B CN112547111 B CN 112547111B CN 202011620025 A CN202011620025 A CN 202011620025A CN 112547111 B CN112547111 B CN 112547111B
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- ruthenium
- benzene
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- microemulsion
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 31
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 51
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 78
- 230000009467 reduction Effects 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 150000003303 ruthenium Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 abstract description 25
- 239000011593 sulfur Substances 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 8
- 150000003568 thioethers Chemical class 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 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
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01J35/396—
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- B01J35/398—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a ruthenium catalyst for removing trace sulfide in benzene, which comprises an active component, an auxiliary agent and a porous carrier, wherein the auxiliary agent and the active component are wrapped by the porous carrier to form a core-shell structure, the active component is ruthenium, the auxiliary agent is one or more of cerium oxide, cobalt oxide, silver oxide and iron oxide, the porous carrier is a ZSM-5 molecular sieve, CO-520 and cyclohexane are added in the preparation of the active component, an auxiliary agent precipitate and a ZSM-5 molecular sieve precursor to form microemulsion, so that groups in the precursor of the generated active component and the auxiliary agent precipitate are combined with hydroxyl groups and the like of the generated molecular sieve to form the catalyst, and the catalyst prepared by the method has the characteristics of high sulfur capacity, small loss of active metal, reproducibility and easy realization of industrial production, can be directly applied to the fine removal process of the partial hydrogenation process of the benzene without changing the working condition.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a ruthenium catalyst for removing trace sulfides in benzene.
Background
Nylon-66 and nylon-6 are both monomers of polyamides. Polyamide is a raw material of synthetic fibers, artificial rubber and engineering plastics closely related to national economic development. At present, nylon-66 and nylon-6 produced at home and abroad are still the complete benzene hydrogenation process route commonly adopted. The traditional process route has the advantages of long process flow, multiple steps, low yield and high energy consumption. In the process, a trace amount of sulfur easily poisons a benzene partial hydrogenation catalyst, so that the activity and selectivity of the catalyst are greatly reduced. In the production process of petroleum refined benzene or coking refined benzene, although series of sulfide removal works are carried out, such as extractive distillation by using sulfolane, formylmorpholine and the like as solvents and critical hydrodesulfurization gradually popularized in recent years, the removal of trace sulfur in the refined benzene to a level which cannot be detected by the existing testing means can not be achieved, and therefore, a fine desulfurization process needs to be added in the hydrogenation process route of the benzene part.
At present, catalysts applied to a fine removal process of a benzene partial hydrogenation process on the market have the defects of needing to change working conditions, being incapable of regeneration or low sulfur capacity, and the frequent replacement or regeneration of an adsorbent is caused.
Disclosure of Invention
The invention aims to provide a ruthenium catalyst for removing trace sulfide in benzene, which has the characteristics of high sulfur capacity, small loss of active metal, reproducibility and easiness in realizing industrial production and can be directly applied to a fine-removing process of a partial hydrogenation process of benzene without changing the working condition.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the ruthenium catalyst comprises an active component, an auxiliary agent and a porous carrier, wherein the auxiliary agent and the active component are wrapped by the porous carrier to form a core-shell structure, the active component is ruthenium, the auxiliary agent is one or more of cerium oxide, cobalt oxide, silver oxide and iron oxide, and the porous carrier is a ZSM-5 molecular sieve.
Further, the mass ratio of the active component to the catalyst is 0.5-3%, the mass ratio of the auxiliary agent to the catalyst is 1-5%, and the balance is a porous carrier.
In the additives, cerium oxide is a first additive, one or more of the rest oxides is a second additive, and the mass ratio of the first additive to the second additive is 1: 1.
the invention also discloses a preparation method of the catalyst, which comprises the following steps:
step 1: adding a first alkali compound into first part of water, stirring, and adding a mixture of water and alkali compound in a volume ratio of 1: continuously and uniformly stirring the CO-520 and the cyclohexane in the step (2-3) to form a microemulsion A;
step 2: adding a proper amount of hydrochloric acid and a second part of water into ruthenium salt and auxiliary agent salt, stirring, and adding the mixture into a reaction kettle according to a volume ratio of 1: continuously and uniformly stirring the CO-520 and the cyclohexane in the step (2-3) to form a microemulsion B;
and step 3: mixing the microemulsion A and the microemulsion B, adding a proper amount of a second alkali compound after stirring for a period of time, slowly adding an organic amine template after continuously stirring for a period of time, and uniformly stirring to obtain a microemulsion C;
and 4, step 4: adding a certain amount of aluminum source compound into the microemulsion C under the stirring action, slowly adding a proper amount of silicon source compound after the aluminum source is uniformly dispersed, continuously stirring until the aluminum source is in a white emulsion state, then transferring the white emulsion state into a hydrothermal synthesis kettle, and crystallizing for a period of time under the hydrothermal synthesis condition;
and 5: carrying out solid-liquid separation, washing, drying and roasting on the crystallized material;
step 6: and reducing the roasted material to obtain the catalyst.
In the raw materials, the aluminum source compound and the silicon source compound are SiO2And Al2O3Meter, SiO2And Al2O3The molar ratio of (80-100) to (1), organic amine template and Al2O3The molar ratio of (4-8): 1, second base compound with Al2O3The molar ratio of (4-8): 1 total water content and Al2O3The molar ratio of (2000-4000): 1.
further, in the step 1, the first alkali compound is sodium hydroxide, potassium hydroxide or concentrated ammonia water.
Further, in the step 2, the ruthenium salt is one or more of ruthenium chloride, ruthenium sulfate and ruthenium nitrate, and the auxiliary salt is one or more of nitrate, sulfate, acetate and chloride.
Further, in the step 3, the second alkalide is sodium hydroxide, potassium hydroxide or concentrated ammonia water, and the organic amine template is tetrapropylammonium hydroxide.
Further, in the step 4, the hydrothermal synthesis condition is crystallization at 150-170 ℃ for 48-72 h.
Further, heating to 50-100 ℃ at the speed of 1-15 ℃/min during drying in the step 5, and drying for 1-5 h; when in roasting, the temperature is raised from room temperature to 150-700 ℃ at the speed of 1-15 ℃/min for 2-10 h.
Further, the reduction in step 6 includes gas phase reduction or liquid phase reduction; introducing hydrogen, carbon monoxide or ethylene during gas phase reduction, wherein the temperature is 80-200 ℃, the reduction time is 1-10h, the temperature is 120-160 ℃, and the space velocity is not more than 6; the pH value is controlled to be 8-12 during liquid phase reduction, and sodium borohydride, hydrazine hydrate, aldehydes, carboxylic acids or olefins are adopted.
Compared with the prior art, the invention has the following beneficial effects:
1) in the preparation process, CO-520 and cyclohexane are added to form microemulsion, so that the generated active component is combined with groups in a precursor of the auxiliary precipitation and hydroxyl groups of the generated molecular sieve, and the like, thereby forming the core-shell catalyst; 2) the catalyst has a step catalysis function, when in desulfurization, only sulfide can enter a pore channel of a ZSM-5 molecular sieve by utilizing the selectivity and the adsorption characteristic of the ZSM-5 molecular sieve, so that the desulfurization selectivity is improved, and then the sulfide is adsorbed by utilizing the high specific surface area and the super adsorption characteristic of a high-dispersion active component ruthenium, so that trace sulfide in benzene can be removed to the extent that the trace sulfide cannot be detected by the conventional analysis means, which is difficult to achieve when the conventional desulfurization active component is loaded on a porous carrier; 3) the molecular sieve structure protects the active and auxiliary components, so that the adsorbed sulfur compound is not easy to desorb, and the active component is not easy to lose in the use process, thereby further improving the desulfurization efficiency and prolonging the service life of the catalyst.
Drawings
FIG. 1 is a TEM image of a catalyst of the present invention;
figure 2 is an XRD pattern of the catalyst of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention is described in detail below with reference to specific examples and experimental data, and it should be understood that the specific examples described herein are only for explaining the present invention and are not intended to limit the present invention.
The invention discloses a ruthenium catalyst for removing trace sulfide in benzene, which comprises an active component, an auxiliary agent and a porous carrier, wherein the auxiliary agent and the active component are wrapped by the porous carrier to form a core-shell structure, the active component is ruthenium, the auxiliary agent is one or more of cerium oxide, cobalt oxide, silver oxide and iron oxide, and the porous carrier is a ZSM-5 molecular sieve.
When the catalyst is applied to removing trace sulfides in benzene, firstly, the selectivity and the adsorption characteristic of a ZSM-5 molecular sieve are utilized, only sulfides can enter a pore channel of the ZSM-5 molecular sieve, so that the selectivity of desulfurization is improved, and then, the sulfides are adsorbed by utilizing the high specific surface area and the super adsorption characteristic of a high-dispersion active component ruthenium, so that the trace sulfides in the benzene can be removed to the extent that the trace sulfides cannot be detected by the conventional analysis means, which is difficult to achieve when the conventional desulfurization active component is loaded on a porous carrier.
As an alternative, the mass ratio of the active component in the catalyst is 0.5-3%, the mass ratio of the auxiliary agent in the catalyst is 1-5%, and the balance is a porous carrier.
Optionally, the cerium oxide is a first aid, one or more of cobalt oxide, silver oxide and iron oxide is a second aid, and the mass ratio of the first aid to the second aid is 1: 1, as a preferred option, to increase the specific surface area of the active component, thereby increasing the sulfur capacity.
The invention also discloses a method for removing trace sulfide in benzene by using the ruthenium catalyst, which comprises the following steps:
step 1: adding a first alkali compound into first part of water, stirring, and adding a mixture of water and alkali compound in a volume ratio of 1: continuously and uniformly stirring the CO-520 and the cyclohexane in the step (2-3) to form a microemulsion A;
step 2: adding a proper amount of hydrochloric acid and a second part of water into ruthenium salt and auxiliary agent salt, stirring, and adding the mixture into a reaction kettle according to a volume ratio of 1: continuously and uniformly stirring the CO-520 and the cyclohexane in the step (2-3) to form a microemulsion B;
and step 3: mixing the microemulsion A and the microemulsion B, adding a proper amount of a second alkali compound after stirring for a period of time, slowly adding an organic amine template after continuously stirring for a period of time, and uniformly stirring to obtain a microemulsion C;
and 4, step 4: adding a certain amount of aluminum source compound into the microemulsion C under the stirring action, slowly adding a proper amount of silicon source compound after the aluminum source is uniformly dispersed, continuously stirring until the aluminum source is in a white emulsion state, then transferring the white emulsion state into a hydrothermal synthesis kettle, and crystallizing for a period of time under the hydrothermal synthesis condition;
and 5: carrying out solid-liquid separation, washing, drying and roasting on the crystallized material;
step 6: and reducing the roasted material to obtain the catalyst.
In the raw materials, the aluminum source compound and the silicon source compound are SiO2And Al2O3Meter, SiO2And Al2O3The molar ratio of (80-100) to (1), organic amine template and Al2O3The molar ratio of (4-8): 1, second base compound with Al2O3The molar ratio of (4-8): 1 total water content and Al2O3The molar ratio of (2000-4000): 1.
CO-520 and cyclohexane are added in the preparation process to form microemulsion, so that the generated active component is combined with the groups in the precursor precipitated by the aid and the hydroxyl groups of the generated molecular sieve, and the core-shell catalyst is formed.
In some embodiments, the first base compound in step 1 may be selected from sodium hydroxide, potassium hydroxide or concentrated ammonia, preferably sodium hydroxide, to ensure the formation of a precursor for the active component and the builder precipitate.
In some embodiments, the ruthenium salt in step 2 is one or more of ruthenium chloride, ruthenium sulfate, and ruthenium nitrate, preferably ruthenium chloride, and the promoter salt can be one or more of nitrate, sulfate, acetate, and chloride, preferably nitrate.
In some embodiments, the second alkali compound in step 3 can be selected from sodium hydroxide, potassium hydroxide or concentrated ammonia, preferably concentrated ammonia, and the organic amine template is preferably tetrapropylammonium hydroxide to ensure the formation of the ZSM-5 molecular sieve.
In some embodiments, the aluminum source compound may be selected from one or more of aluminum sulfate, sodium aluminate, aluminum nitrate, aluminum isopropoxide, preferably aluminum isopropoxide, and the silicon source compound may be selected from one or more of silica sol, methyl orthosilicate, and ethyl orthosilicate, preferably ethyl orthosilicate.
In some embodiments, the hydrothermal synthesis conditions in step 4 may be selected from 150-170 ℃ for 48-72 h, preferably 150 ℃ for 72h, to ensure the formation of the ZSM-5 molecular sieve.
In some embodiments, the drying in step 5 may be performed by heating to 50-100 ℃ at a rate of 1-15 ℃/min for 1-5h, preferably at a rate of 5 ℃/min for 2 h; the heat treatment can be carried out for 2-10 h from room temperature to 150-700 ℃ at the temperature of 1-15 ℃/min, preferably for 5h from room temperature to 500 ℃ at the temperature of 5 ℃/min, so that the uniform heating of the catalyst precursor in the heat treatment process is ensured, the phenomena of cracking and the like of the wet-based granular catalyst caused by rapid heating are prevented, and more importantly, the good dispersion state of the active metal component ruthenium atoms in the catalyst is ensured.
In some embodiments, the reduction in step 6 can be selected from gas phase reduction or liquid phase reduction, wherein hydrogen, carbon monoxide or ethylene is introduced during the gas phase reduction at 80-200 ℃, the reduction time is 1-10h, the temperature is 120--1(ii) a And (2) controlling the pH value to be 8-12 during liquid-phase reduction, adopting sodium borohydride, hydrazine hydrate, aldehydes, carboxylic acids or olefins, preferably carrying out gas-phase reduction, wherein the volume ratio of the reduction atmosphere is 30: 70 of mixed gas of nitrogen and hydrogen, the reduction temperature is 100 ℃, the reduction time is 2 hours, and the space velocity is 6 hours-1(ii) a To ensure that the ruthenium oxide is reduced to metallic ruthenium and that the sulphide can be adsorbed.
The present invention is described in detail below with reference to specific examples. The desulfurization performance of the catalyst was evaluated by using a small fixed bed reactor with a 50 g loading, and the sulfide contents in the feed aromatic hydrocarbon and the discharge aromatic hydrocarbon were analyzed by using a total sulfur analyzer and a gas chromatograph.
Example 1
Adding 2.7g of NaOH into 400ml of water, stirring, adding 800ml of CO-520 and 1600 ml of cyclohexane after dissolving, and continuously stirring uniformly to form a microemulsion A, adding 1.0g of ruthenium chloride, 5.4 g of cerous nitrate hexahydrate and 2.1g of silver nitrate into 300ml of water, stirring, adding 1200 ml of CO-520 and 2400 ml of cyclohexane after dissolving, and continuously stirring uniformly to form a microemulsion B, mixing the microemulsion A and the microemulsion B, adding 12 ml of concentrated ammonia water after stirring for a period of time, slowly adding 15.7g of TPAOH after continuously stirring for a period of time, and stirring uniformly to obtain a microemulsion C, adding 7.9 g of aluminum isopropoxide into the microemulsion C under the stirring action, slowly adding 320 g of TEOS after the aluminum isopropoxide is uniformly dispersed, continuously stirring to a white emulsion state, and then transferring to a hydrothermal synthesis kettle for crystallization at 150 ℃ for 72 hours; carrying out solid-liquid separation and washing on the crystallized material, putting the washed material into a drying oven, and heating to 100 ℃ at the speed of 5 ℃/min and drying for 2 h; then heating the dried material from room temperature to 500 ℃ at the speed of 5 ℃/min for 5 h; placing the heat-treated material into a fixed bed reactor, performing nitrogen replacement on the reactor, performing gas phase reduction at 100 ℃ by using mixed gas with the volume ratio of nitrogen to hydrogen being 30: 70, wherein the reduction holding time is 2 hours, and the airspeed is 6 hours-1Is reduced to obtain removalA ruthenium catalyst containing a trace amount of sulfide in benzene was designated as sample 1.
Example 2
Adding 2.9 g of NaOH into 650ml of water and stirring, adding 850ml of CO-520 and 2550 ml of cyclohexane after dissolving, and continuously stirring uniformly to form a microemulsion A, adding 2.1g of ruthenium chloride, 5.4 g of cerous nitrate hexahydrate and 2.1g of silver nitrate into 450ml of water and stirring, adding 850ml of CO-520 and 2550 ml of cyclohexane after dissolving, and continuously stirring uniformly to form a microemulsion B, mixing the microemulsion A and the microemulsion B, adding 19 ml of concentrated ammonia water after stirring for a period of time, slowly adding 25.0g of TPAOH after continuously stirring for a period of time, and uniformly stirring to obtain a microemulsion C, adding 6.3 g of aluminum isopropoxide into the microemulsion C under the stirring action, slowly adding 320 g of TEOS after the aluminum isopropoxide is uniformly dispersed, continuously stirring to a white emulsion state, then transferring to a hydrothermal synthesis kettle, and crystallizing for 72 hours at 150 ℃; carrying out solid-liquid separation and washing on the crystallized material, putting the washed material into a drying oven, and heating to 100 ℃ at the speed of 5 ℃/min and drying for 2 h; then heating the dried material from room temperature to 500 ℃ at the speed of 5 ℃/min for 5 h; placing the heat-treated material into a fixed bed reactor, performing nitrogen replacement on the reactor, performing gas phase reduction at 100 ℃ by using mixed gas with the volume ratio of nitrogen to hydrogen being 30: 70, wherein the reduction holding time is 2 hours, and the airspeed is 6 hours-1The ruthenium catalyst from which trace amount of sulfide in benzene was removed was obtained after reduction, and the catalyst was labeled as sample 2.
Example 3
Adding 3.0 g of NaOH into 500ml of water, stirring, adding 800ml of CO-520 and 2000ml of cyclohexane after dissolving, continuously stirring uniformly to form a microemulsion A, adding 4.1 g of ruthenium chloride, 5.3 g of cerous nitrate hexahydrate and 3.5g of cobalt nitrate hexahydrate into 400ml of water, stirring, adding 850ml of CO-520 and 2000ml of cyclohexane after dissolving, continuously stirring uniformly to form a microemulsion B, mixing the microemulsion A and the microemulsion B, adding 12 ml of concentrated ammonia water after stirring for a period of time, slowly adding 21g of TPAOH after continuously stirring for a period of time, and stirring uniformly to obtain a microemulsion C, adding 7.0 g of aluminum isopropoxide into the microemulsion C under the stirring action, slowly adding 323 g of TEOS after the aluminum isopropoxide is uniformly dispersed, continuously stirring to be in a white emulsion state, and then transferring to waterCrystallizing for 72 hours at 150 ℃ in a thermal synthesis kettle; carrying out solid-liquid separation and washing on the crystallized material, putting the washed material into a drying oven, and heating to 100 ℃ at the speed of 5 ℃/min and drying for 2 h; then heating the dried material from room temperature to 500 ℃ at the speed of 5 ℃/min for 5 h; placing the heat-treated material into a fixed bed reactor, performing nitrogen replacement on the reactor, performing gas phase reduction at 100 ℃ by using mixed gas with the volume ratio of nitrogen to hydrogen being 30: 70, wherein the reduction holding time is 2 hours, and the airspeed is 6 hours-1The ruthenium catalyst from which trace amount of sulfide in benzene was removed was obtained after reduction, and the catalyst was labeled as sample 3.
Example 4
Adding 2.6 g of NaOH into 500ml of water and stirring, adding 800ml of CO-520 and 2000ml of cyclohexane after dissolving, continuously stirring uniformly to form a microemulsion A, adding 6.2 g of ruthenium chloride, 9.8 g of cerous nitrate hexahydrate and 9.1g of ferric nitrate nonahydrate into 400ml of water and stirring, adding 850ml of CO-520 and 2000ml of cyclohexane after dissolving, continuously stirring uniformly to form a microemulsion B, mixing the microemulsion A and the microemulsion B, adding 16 ml of concentrated ammonia water after stirring for a period of time, slowly adding 24.8g of TPAOH after continuously stirring for a period of time, and stirring uniformly to obtain a microemulsion C, adding 7.1 g of aluminum isopropoxide into the microemulsion C under the stirring action, slowly adding 327 g of TEOS after the aluminum isopropoxide is uniformly dispersed, continuously stirring to be in a white emulsion state, then transferring to a hydrothermal synthesis kettle, and crystallizing for 72 hours at 150 ℃; carrying out solid-liquid separation and washing on the crystallized material, putting the washed material into a drying oven, and heating to 100 ℃ at the speed of 5 ℃/min and drying for 2 h; then heating the dried material from room temperature to 500 ℃ at the speed of 5 ℃/min for 5 h; placing the heat-treated material into a fixed bed reactor, performing nitrogen replacement on the reactor, performing gas phase reduction at 100 ℃ by using mixed gas with the volume ratio of nitrogen to hydrogen being 30: 70, wherein the reduction holding time is 2 hours, and the airspeed is 6 hours-1The ruthenium catalyst from which trace amount of sulfide in benzene was removed was obtained after reduction, and the catalyst was labeled as sample 4.
Example 5
The procedure is as in example 1, except that 2.1g of silver nitrate is replaced by 7.2 g of cerium nitrate hexahydrate, otherwise the catalyst is identical to that of example 1 and is designated sample 5
Comparative example 1
The preparation was identical to example 1, except that no CO-520 and cyclohexane were added during the preparation, and this catalyst sample was labeled as comparative sample 1.
Comparative example 2
The preparation was identical to example 1, except that cerium nitrate hexahydrate and silver nitrate were not added during the preparation, otherwise identical to example 1, and the catalyst sample was labeled as comparative sample 2.
Comparative example 3
Adding 7.9 g of aluminum isopropoxide into the microemulsion C under the stirring action, slowly adding 320 g of TEOS after the aluminum isopropoxide is uniformly dispersed, continuously stirring until the mixture is in a white emulsion state, then transferring the mixture into a hydrothermal synthesis kettle, and crystallizing for 72 hours at 150 ℃; carrying out solid-liquid separation and washing on the crystallized material, putting the washed material into a drying oven, and heating to 100 ℃ at the speed of 5 ℃/min and drying for 2 h; and then heating the dried material from room temperature to 500 ℃ at the speed of 5 ℃/min for 5h to obtain the ZSM-5 molecular sieve, placing the ZSM-5 molecular sieve in a beaker, adding 50ml of water, and stirring to form a suspension A.
Adding 2.7g of NaOH into 50ml of water and stirring to form a solution B, adding 1.0g of ruthenium chloride, 5.4 g of cerous nitrate hexahydrate and 2.1g of silver nitrate into 50ml of water and stirring to form a solution C, simultaneously adding the solution B and the solution C into the suspension A and stirring, after the reaction is finished, carrying out solid-liquid separation and washing on the materials, putting the washed materials into a drying oven, and heating to 100 ℃ at the speed of 5 ℃/min and drying for 2 h; then heating the dried material from room temperature to 500 ℃ at the speed of 5 ℃/min for heat treatment for 5h, putting the heat-treated material into a fixed bed reactor, carrying out nitrogen replacement on the reactor, then carrying out gas phase reduction at the temperature of 100 ℃ by using mixed gas of nitrogen and hydrogen with the volume ratio of 30 to 70, wherein the reduction holding time is 2 hours, and the airspeed is 6h-1The ruthenium catalyst from which trace amount of sulfide in benzene was removed was obtained after reduction, and the catalyst was labeled as comparative sample 3.
Comparative example 4
2.7g NaOH are added to 400ml water and stirred untilDissolving, adding 800ml CO-520 and 1600 ml cyclohexane, stirring to form microemulsion A, adding 1.0g ruthenium chloride, 5.4 g cerous nitrate hexahydrate and 2.1g silver nitrate into 300ml water, stirring, adding 1200 ml CO-520 and 2400 ml cyclohexane, stirring to form microemulsion B, mixing microemulsion A and microemulsion B, stirring for a period of time, adding 12 ml strong ammonia water, stirring for a period of time, slowly adding 328 g TEOS, stirring to white emulsion, and stirring for 48h to make SiO in emulsion2Crystallizing; carrying out solid-liquid separation and washing on the crystallized material, putting the washed material into a drying oven, and heating to 100 ℃ at the speed of 5 ℃/min and drying for 2 h; then heating the dried material from room temperature to 500 ℃ at the speed of 5 ℃/min for 5 h; placing the heat-treated material into a fixed bed reactor, performing nitrogen replacement on the reactor, performing gas phase reduction at 100 ℃ by using mixed gas with the volume ratio of nitrogen to hydrogen being 30: 70, wherein the reduction holding time is 2 hours, and the airspeed is 6 hours-1And the ruthenium catalyst from which trace amount of sulfide in benzene was removed was obtained after reduction, and the catalyst was labeled as comparative sample 4.
Comparative sample 5
Adding 7.9 g of aluminum isopropoxide into the microemulsion C under the stirring action, slowly adding 320 g of TEOS after the aluminum isopropoxide is uniformly dispersed, continuously stirring until the mixture is in a white emulsion state, then transferring the mixture into a hydrothermal synthesis kettle, and crystallizing for 72 hours at 150 ℃; carrying out solid-liquid separation and washing on the crystallized material, putting the washed material into a drying oven, and heating to 100 ℃ at the speed of 5 ℃/min and drying for 2 h; and then heating the dried material from room temperature to 500 ℃ at the speed of 5 ℃/min for 5h to obtain the ZSM-5 molecular sieve, and marking the catalyst as a comparative sample 5.
The above examples and comparative examples were evaluated for desulfurization performance by the following methods:
50 g of the catalyst prepared by the method is filled into a fixed bed reactor with the height-diameter ratio of 4.5 and the effective volume of 70ml, and a small amount of activated alumina with the same specification is filled at the two ends of the fixed bed reactor; sulfur-free benzene was used to formulate a feed benzene having a sulfur content (thiophene) of 3 wtppm. Fixed bedThe reactor is heated to 118-122 ℃ at a liquid space velocity of 3.5 h-1And adjusting the flow rate of the constant flow pump. After the preparation work is ready, the transverse flow pump is started to carry out a deep desulfurization test, and the reaction pressure is maintained at 0.1 MPa. The reactor outlet sulfide concentration was monitored at a frequency of times/4 hours until the reactor outlet sulfide concentration was 0.01wtppm, and the amount of benzene actually consumed as the sulfur-containing feed was recorded.
The sulfide removal capacity (sulfur capacity: g sulfide/kg catalyst) of the catalyst was calculated from the amount of catalyst used and the total amount of sulfide, and the results are shown in Table 1.
TABLE 1 comparison of sulfur capacity of samples of each catalyst
As can be seen from Table 1, the sulfur capacity of the core-shell catalyst prepared by the method is more than 1.7 g (thiophene)/kg (cat), and the sulfur capacity of the comparative sample 1 is only 1.1 g (thiophene)/kg (cat), which shows that the method designs the catalyst into a core-shell structure, effectively improves the selective adsorption of the catalyst on sulfur, and further increases the sulfur capacity, and the sulfur capacity of the sample 5 is lower than that of the samples of other examples, which shows that the sulfur capacity of the catalyst can be improved when two additives are mixed; the comparative sample 2 is a core-shell catalyst without an additive, and the sulfur capacity of the core-shell catalyst is 1.4 g (thiophene)/kg (cat), which is much lower than that of the sample 1, which shows that the additive can effectively improve the sulfur capacity; the comparative sample 3 is a ZSM-5 molecular sieve synthesized firstly, and then active components and auxiliary agents are precipitated on the pore passages or the outer surfaces of the molecular sieve, the preparation method is similar to the impregnation method, and the sulfur capacity of the catalyst prepared by the method is far lower than that of the catalyst prepared by the invention; comparative sample 4 also had a core-shell structure, but the material covered with it was pure SiO2The sulfur capacity of the molecular sieve is not as good as that of the ZSM-5 molecular sieve wrapped by the invention, which shows that the sulfur capacity is related to the structure of the wrapping material, and the comparative sample 5 is a pure ZSM-5 molecular sieve, the sulfur capacity of which is 0.8 g (thiophene)/kg (cat), which shows that the ZSM-5 molecular sieve has certain capacity of adsorbing sulfides, but the sulfur capacity of which is lower than that of the catalyst of the invention, which shows that the sulfur capacity of the catalyst of the invention is improved by the improved design of the inventionSulfur capacity.
The catalyst after reaction can be desorbed under the condition of pressure reduction or vacuum pumping, and can be matched with inert gas purging to improve the desorption effect and quickly realize the regeneration of the catalyst. Due to the protection effect of the molecular sieve on the active component and the auxiliary agent, the catalyst can be repeatedly regenerated and used for many times, and has longer service life compared with the traditional adsorbent.
In order to verify that the catalyst prepared by the invention has a core-shell structure and the outer layer is wrapped by the ZSM-5 molecular sieve, a sample in the embodiment 1 is subjected to TEM and XRD characterization, the TEM result is shown in figure 1 and the XRD result is shown in figure 2, as can be seen from figure 1, the catalyst with the core-shell structure can be synthesized by adopting the preparation method disclosed by the invention, as can be seen from figure 2, the molecular sieve with the shell structure being ZSM-5 is successfully synthesized, and the active component and the auxiliary agent cannot be displayed in an XRD spectrogram due to the wrapping.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The ruthenium catalyst for removing trace sulfide in benzene is characterized by comprising an active component, an auxiliary agent and a porous carrier, wherein the auxiliary agent and the active component are wrapped by the porous carrier to form a core-shell structure, the active component is ruthenium, the auxiliary agent is one or more of cerium oxide, cobalt oxide, silver oxide and iron oxide, and the porous carrier is a ZSM-5 molecular sieve; the preparation method of the catalyst comprises the following steps:
step 1: adding a first alkali compound into first part of water, stirring, and adding a mixture of water and alkali compound in a volume ratio of 1: continuously and uniformly stirring the CO-520 and the cyclohexane in the step (2-3) to form a microemulsion A;
step 2: adding a proper amount of hydrochloric acid and a second part of water into ruthenium salt and auxiliary agent salt, stirring, and adding the mixture into a reaction kettle according to a volume ratio of 1: continuously and uniformly stirring the CO-520 and the cyclohexane in the step (2-3) to form a microemulsion B;
and step 3: mixing the microemulsion A and the microemulsion B, adding a proper amount of a second alkali compound after stirring for a period of time, slowly adding an organic amine template after continuously stirring for a period of time, and uniformly stirring to obtain a microemulsion C;
and 4, step 4: adding a certain amount of aluminum source compound into the microemulsion C under the stirring action, slowly adding a proper amount of silicon source compound after the aluminum source is uniformly dispersed, continuously stirring until the aluminum source is in a white emulsion state, then transferring the white emulsion state into a hydrothermal synthesis kettle, and crystallizing for a period of time under the hydrothermal synthesis condition;
and 5: carrying out solid-liquid separation, washing, drying and roasting on the crystallized material;
step 6: and reducing the roasted material to obtain the catalyst.
2. The ruthenium catalyst for removing trace sulfide in benzene as claimed in claim 1, wherein the mass ratio of the active component in the catalyst is 0.5-3%, the mass ratio of the auxiliary in the catalyst is 1-5%, and the balance is porous carrier.
3. The ruthenium-based catalyst for removing trace sulfide in benzene as claimed in claim 1, wherein cerium oxide is a first promoter, one or more of the remaining oxides is a second promoter, and the mass ratio of the first promoter to the second promoter is 1: 1.
4. the ruthenium catalyst for removing trace sulfide from benzene as claimed in any one of claims 1 to 3, wherein the aluminum source compound and the silicon source compound in the raw material are SiO2And Al2O3Meter, SiO2And Al2O3The molar ratio of (80-100) to (1), organic amine template and Al2O3The molar ratio of (4-8): 1, second base compound with Al2O3The molar ratio of (4-8): 1 total water content and Al2O3The molar ratio of (2000-4000): 1.
5. the ruthenium-based catalyst for removing trace sulfide from benzene according to any one of claims 1 to 3, wherein the first alkali compound in step 1 is sodium hydroxide, potassium hydroxide or concentrated aqueous ammonia.
6. A ruthenium catalyst according to any one of claims 1 to 3 for removing trace amounts of sulfide from benzene, wherein the ruthenium salt in step 2 is one or more of ruthenium chloride, ruthenium sulfate and ruthenium nitrate, and the auxiliary salt is one or more of nitrate, sulfate, acetate and chloride.
7. The ruthenium catalyst according to any one of claims 1 to 3, wherein the second base compound in step 3 is sodium hydroxide, potassium hydroxide or concentrated ammonia, and the organic amine template is tetrapropylammonium hydroxide.
8. The ruthenium catalyst for removing trace sulfide from benzene according to any one of claims 1 to 3, wherein the hydrothermal synthesis in step 4 is performed at 150 to 170 ℃ for 48 to 72 hours.
9. The ruthenium catalyst according to any one of claims 1 to 3 for removing trace sulfide from benzene, wherein the temperature is raised to 50 to 100 ℃ at a rate of 1 to 15 ℃/min and the catalyst is dried for 1 to 5 hours in the step 5; when in roasting, the temperature is raised from room temperature to 150-700 ℃ at the speed of 1-15 ℃/min for 2-10 h.
10. The ruthenium-based catalyst for removing trace sulfide from benzene according to any one of claims 1 to 3, wherein the reduction in step 6 comprises gas phase reduction or liquid phase reduction; introducing hydrogen, carbon monoxide or ethylene during gas phase reduction, wherein the temperature is 80-200 ℃, the reduction time is 1-10h, the temperature is 120-160 ℃, and the space velocity is not more than 6; the pH value is controlled to be 8-12 during liquid phase reduction, and sodium borohydride, hydrazine hydrate, aldehydes, carboxylic acids or olefins are adopted.
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Citations (2)
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| CN109261201A (en) * | 2018-10-23 | 2019-01-25 | 太原理工大学 | A kind of hud typed hydrogenation catalyst and preparation method thereof |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104998657A (en) * | 2015-06-29 | 2015-10-28 | 重庆华峰化工有限公司 | Catalyst for refined removal of trace amount of sulfides in benzene and its preparation method and use |
| CN104998657B (en) * | 2015-06-29 | 2018-01-30 | 重庆华峰化工有限公司 | Catalyst of trace sulfide and its preparation method and application in essence removing benzene |
| CN109261201A (en) * | 2018-10-23 | 2019-01-25 | 太原理工大学 | A kind of hud typed hydrogenation catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of Rh nanoparticles encapsulated in ZSM-5 and its application for methanol to olefn over acid sites with simultaneous production of hydrogen over Rh;Hiroyasu Fujitsuka et al.;《Catalysis Today》;20200430;摘要，第6-7页 * |
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