CN109420507A - A kind of Hydrobon catalyst and preparation method thereof containing macropore alumina supporter - Google Patents
A kind of Hydrobon catalyst and preparation method thereof containing macropore alumina supporter Download PDFInfo
- Publication number
- CN109420507A CN109420507A CN201710768137.5A CN201710768137A CN109420507A CN 109420507 A CN109420507 A CN 109420507A CN 201710768137 A CN201710768137 A CN 201710768137A CN 109420507 A CN109420507 A CN 109420507A
- Authority
- CN
- China
- Prior art keywords
- alumina support
- potassium
- macropore
- strontium
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims description 37
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 39
- 239000000839 emulsion Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 32
- 229910001593 boehmite Inorganic materials 0.000 claims description 31
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 31
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 30
- 239000011591 potassium Substances 0.000 claims description 30
- 229910052700 potassium Inorganic materials 0.000 claims description 29
- 229910052712 strontium Inorganic materials 0.000 claims description 26
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 26
- -1 93-99wt% Chemical compound 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 20
- 241000219782 Sesbania Species 0.000 claims description 19
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 18
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 18
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 238000002803 maceration Methods 0.000 claims description 13
- 230000008859 change Effects 0.000 claims description 12
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000004323 potassium nitrate Substances 0.000 claims description 9
- 235000010333 potassium nitrate Nutrition 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000006210 lotion Substances 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- 238000000034 method Methods 0.000 description 33
- 239000008367 deionised water Substances 0.000 description 27
- 229910021641 deionized water Inorganic materials 0.000 description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- 239000011148 porous material Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000002738 chelating agent Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 241000219793 Trifolium Species 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 238000004945 emulsification Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 8
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012018 catalyst precursor Substances 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920002379 silicone rubber Polymers 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 6
- 239000012876 carrier material Substances 0.000 description 6
- 229940011182 cobalt acetate Drugs 0.000 description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000006071 cream Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000003573 thiols Chemical class 0.000 description 6
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004966 Carbon aerogel Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
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- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 2
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- 239000011805 ball Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of catalyst for selectively hydrodesulfurizing containing macropore alumina supporter, it is formed with oxidation material meter, including following component: the alumina support containing macropore is 82-95wt%, oxidation molybdenum content is 2-14wt%, cobalt oxide content is 1-5wt%, the catalyst is used for catalytic gasoline hydrogenation desulfurization, can solve the problems, such as that desulfurization degree existing in the prior art is low, desulfuration selectivity is poor and loss of octane number is big.
Description
Technical field
The present invention relates to a kind of catalyst for selectively hydrodesulfurizing and preparation method thereof containing macropore alumina supporter, belongs to
Oil hydrogenation catalyst for refining preparation technical field.
Background technique
In recent years, with the rapid development of auto industry, global auto recoverable amount is sharply increased, the nocuousness of motor vehicle exhaust emission
Problem of environmental pollution caused by object is gradually of interest by people.In order to reduce the discharge amount of nuisance in vehicle exhaust,
Countries in the world propose requirement higher and higher to the quality of vehicle fuel.At the same time, China also accelerates quality of gasoline liter
The paces of grade, to can mutually integrate with international advanced motor petrol standard level in a relatively short period of time.
It is different with foreign countries, in China's gasoline pool, the catalytically cracked gasoline (FCC gasoline) of high-sulfur, high olefin content
Account for about 70%, therefore, the key of domestic quality of gasoline upgrading is that cleaning for FCC gasoline, i.e. sulphur in reduction FCC gasoline
Content and control olefin(e) centent.Although can effectively realize the mesh of FCC gasoline desulfurating and reducing olefinic hydrocarbon using traditional hydrodesulfurization technology
Mark, but alkene excessive hydrogenation is easily caused to be saturated, loss of octane number is larger, so be difficult to be received by refinery.For this purpose, some new
Desulfurization technology come into being, wherein selective hydrodesulfurization technology is most representative.
For selective hydrodesulfurization technology, it is de- to develop a kind of with greater activity and good selectivity plus hydrogen
Matched sulfur catalyst is one of key technology.Currently, the catalyst for oil product selective hydrodesulfurization reaction is main
For loaded catalyst again, wherein the selection of carrier material becomes the basis of the catalyst R&D work with preparation.Carrier conduct
The important component of loaded catalyst, other than it can improve active component dispersibility, cellular structure can be also reaction
Object and product molecule provide diffusion admittance, to improve active component utilization rate.Based on These characteristics possessed by carrier, in conjunction with
Oil product selective hydrodesulfurization reaction process, according to the difference of reactants and products molecular dimension, on current carrier material basis
On develop the carrier material with reasonable macroporous structure, so that it may from mass transfer angle, effectively reduce resistance to mass tranfer and increase
Mass transfer rate, so as to improve the performance of catalyst.Therefore, there is the carrier material of reasonable macroporous structure to become such for exploitation
The research hotspot and development trend of catalyst upgrading.
Aluminium oxide as traditional catalyst carrier material, have that technology maturation, pore structure are adjustable, use cost is low and
The features such as being easily worked molding is widely used in the preparation of oil-refining chemical catalyst.According to differential responses to cellular structure and table
The requirement of face acidity, has formd miscellaneous process for making alumina and product, such as improving aluminium oxide and activity gold
The composite aluminas product such as titaniferous, zirconium for being acted between category；For improving the oxidation such as the fluorine-containing of Surface Acidity of Alumina Support, chlorine
Aluminium product；And the alumina products such as high heap ratio, low heap ratio, high-specific surface area, high-purity.The cellular structure of aluminium oxide derives from
Particle or intergranular accumulation gap, the gama-alumina aperture that conventional method synthesizes is generally less than 15nm, although Recent study
Persons have carried out a large amount of research work, but the commercially available aluminium oxide containing macroporous structure in terms of macroporous structure aluminium oxide synthesis
Product is still less.
In order to obtain containing the alumina supporting material of macroporous structure, researchers are by using template, hydro-thermal process etc.
Method obtains the aluminium oxide of macroporous structure.Wherein, existing very using the pertinent literature of template method macroporous aluminium oxide material
It is more, according to the difference of Template Types, hard mould agent and two kinds of soft template can be divided into.Using active carbon as the hard template of representative
The available preferable macroporous aluminium oxide of agent method, US4448896 disclose a kind of carbon black as expanding agent, available aperture point
Cloth 15-300nm macroporous aluminium oxide, but since the particle diameter distribution of carbon black is inhomogenous, it is more difficult to prepare pore-size distribution collection
In macroporous aluminium oxide.CN201410347665.X disclose a kind of macropore hold, the preparation method of high-strength alumina, by adding
Enter the expanding agents such as polyacrylamide, polyvinyl alcohol, alkylcellulose, sesbania powder, starch, obtains containing eurypyloue carrying alumina
Body, the dosage of expanding agent account for the 10-30% of aluminium oxide, but not publicly specific pore diameter range.Although hard mould agent method can be with
Preferable macropore alumina supporter is obtained, but the dosage of its template is larger, to cause processing cost to greatly improve, largely
The decomposition of template does not meet the demand for development of low-carbon environment-friendly yet.CN201010509425.7 discloses a kind of hydro-thermal and template
The method of common reaming is acted on preparing the alumina support containing macroporous structure by the complementary reaming of hydro-thermal, template
Dosage can be down to 3-10%, but auxiliary hydro-thermal causes the raising of energy consumption again at the same time.CN200310103035.X is disclosed
A kind of preparation method of macroporous aluminium oxide carries out reaming using polyvinyl alcohol, poly- propyl alcohol, polyethylene glycol soft template, by adding
Enter 1% polyethylene glycol, Kong Rong of the aperture greater than 100nm accounts for the 26.2% of total pore volume.For hard mould agent, soft template
Agent then has the advantages that dosage is low, reaming effect is prominent, but the dissolution due to the biggish alcohols soft template of molecular weight in water
Property is relatively poor, so that it is restricted when expanding super large porous aluminum oxide.CN201410148773.4 discloses a kind of aluminium oxide
The preparation method of porous microsphere, comprising the following steps: 1) surfactant is dissolved in deionized water, is stirred, as water phase；2)
Chelating agent, alumina precursor are mixed with n-octyl alcohol, stirred, as oily phase；3) Span80 and pore are added in oily phase
Agent, stirring；4) clear oil obtained by step 3) is mutually poured into water phase and continues stirring and emulsifying；5) by step 4) gains vacuum
It filters, it is dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.The microballoon has internal closed macroporous structure, microballoon ruler
Very little is 1-100 μm, which is obtained using the sol-gel process in pore-foaming agent and lotion has internal closing macroporous structure
Metal porous microballoon.Porous microsphere is prepared using phase separation principle.Inside closing aperture is 50nm-5 μm.Pore-foaming agent is polyethylene
Pyrrolidones, polyacrylamide or polyacrylic acid.The invention has used a large amount of surfactant, chelating agent, pore-foaming agent, preparation
Raw material is more, and synthesis technology is complicated.CN201310748661.8 discloses a kind of preparation side of aluminium oxide/carbon aerogel composite material
Water-soluble saccharides compound and water soluble polymer are dissolved in water in closed container by method, and aluminium salt or hydroxide is then added
Aluminium is reacted at 140-300 DEG C, and to obtain aluminium oxide/carbon aerogels compound for calcining under 300-1500 DEG C of inert atmosphere after drying
Material.The invention is had using one kettle way preparation low-density, aluminium oxide/carbon aerogel composite material of high porosity, the present invention
The advantages that raw material is easy to get, preparation process is simple, at low cost, resulting aluminium oxide/carbon aerogel composite material is light, porosity
Height can be used for catalyst carrier, gas sensor, solid electrolytic diaphragm and molten steel oxygen measuring probe material etc..
CN201310499233.6 discloses a kind of preparation method of alumina support, including following content: alkaline precipitating agent is water-soluble first
Liquid and acid aluminium salt aqueous solution carry out neutralization reaction and obtain sediment slurry；Then water-soluble resin is added into sediment slurry and adopts
Aging process is carried out to it with microwave heating；Mixed material after last aging is filtered, washed, dried, form and is made finally
Alumina support.The alumina support of this method preparation has the pore size distribution in biggish aperture and concentration, especially 10-20nm's
Hole accounts for the 60-80% of total pore volume, is suitable for the carrier of heavy-oil hydrogenation catalyst.CN201310258011.5 relates to a kind of tooth
Spherical alumina support, corresponding hydrotreating catalyst and preparation method thereof, including following components: the glue of 0.5-4 parts by weight
Solvent；The lubricant of 0.2-2 parts by weight；The dispersing agent of 0.2-3 parts by weight；The expanding agent of 0.3-4 parts by weight；100 parts by weight
Aluminium hydroxide.Expanding agent is one of polyvinyl alcohol, Sodium Polyacrylate, starch derivatives or carbon black or mixture.The invention
Anionic surfactant being added to while reducing various auxiliary component additive amounts, specific surface area increases 246m2/ g, reaming
Agent uses Sodium Polyacrylate.Tooth spherical alumina support described in the invention, due to considerably reducing various auxiliary agents such as peptization
The content of the components such as agent, expanding agent, dispersing agent, anionic surfactant has not only saved cost, also has specific surface area
Greatly, the advantages that high mechanical strength.The invention has used peptizing agent, lubricant, dispersing agent, the reagents such as expanding agent, and obtained
Alumina support is unimodal pore size distribution.CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and its preparation side
Method.The three-dimensional ordered macroporous alumina, diameter macropores 50-1000nm, grain diameter 1-50mm, mechanical strength 80-
280g/mm.Method includes the following steps: adding saccharide compound and the concentrated sulfuric acid into monodisperse polymer micro-sphere lotion, obtain
To polymer-modified microballoon glue crystal template, it is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous oxygen
Change aluminium.This method can increase substantially the adhesion amount of aluminium oxide precursor, and the mechanical strength of reinforcing material is removed in high-temperature roasting
It is fine-powder that large pore material is not easily broken when template, can still keep higher integrity degree.CN201110116418.5 is provided
A kind of mesoporous sphere aluminium oxide and the method for preparing the mesoporous sphere aluminium oxide is oriented to using template.Using forming oil column
The template with guide function is added in method during preparing Aluminum sol into Aluminum sol, and Aluminum sol is in molding and aging
Cheng Zhong, since the presence of the template with guide function to generate a large amount of meso-hole structure in alumina balls.Template is
Organic monomer or linear polymer, organic monomer are one of acrylic acid, ammonium acrylate, acrylamide or allyl alcohol.Jie
Hole ball-aluminium oxide specific surface area is 150-300m2/ g, particle diameter 0.1-5mm, pore volume 0.7-1.5mL/g, Kong Zhi
The hole that diameter is 2-40nm is greater than 97%, and heap density is 0.3-0.8g/cm3, crushing strength is 70-250N/.The invention utilizes mould
The mesoporous sphere alumina pore diameter of plate agent preparation compares concentration, can be used for petrochemical industry and fine chemistry industry and carries as catalyst
Body or catalyst.
CN201010221302.3 (CN102311134A) discloses a kind of spherical integral macroporous alumina and its preparation side
Method.Method includes the following steps: polymer microballoon lotion, alumina sol and coagulant are mixed in a certain proportion uniformly,
The mixture is scattered in oily phase, w/o type drop is formed, then reheats above-mentioned mixed phase system, make the aluminium oxide in water phase
Colloidal sol gelling balling-up, isolates molding gel micro-ball from oily phase later, then aged, the dry and roasting in aqueous ammonia medium
The spherical integral macroporous alumina is obtained afterwards.The macropore diameter of the aluminium oxide is uniform controllable in the range of less than 1 μm,
The size of spheric granules is controllable, and mechanical strength is higher, and forming process is simple and easy to do, suitable for being prepared on a large scale.Polymer microballoon
Diameter is 50-1000nm, and type is the esters microballoons such as polystyrene microsphere, polyaerylic acid N-butyl microballoon, polyacrylate.Promote
Solidifying agent is hexamethylenetetramine, urea.Oily is mutually organic hydrocarbon.The invention mainly prepares Integral macroporous alumina, and big
Hole aperture is uniform controllable.Preparation process has used lipid microballoon and coagulant etc., and preparation process is relative complex, and agents useful for same is former
Expect many kinds of.Due to having used polymer microballoon that alumina support internal gutter structure is made to be blind bore, that is to say, that
Alumina support internal gutter does not have connectivity.CN200910204238.5 (CN102040235), which discloses a kind of three-dimensional, to be had
Sequence macroporous aluminium oxide and preparation method thereof.Method includes the following steps: monodispersed polymer microballoon is assembled into glue crystalline substance mould
Then plate fills the alumina sol of ad hoc approach preparation into template, most obtain macroporous aluminium oxide through dry and roasting afterwards.It should
Method can be good at controlling the recombination process of Aluminum sol and Aluminum sol and polymer microballoon, and it is solidifying not destroy aluminium oxide as far as possible
The network structure of glue makes prepared aluminium oxide not only and has the macropore duct of three-dimensional order but also specific surface with higher
Product.The small fenestra that the invention is formed and the appropriateness to template is sintered, makes the macropore in material and the macropore of surrounding by 12
A small fenestra is connected.The aluminium oxide of the invention is suitable for use as the adsorbing separation material of mink cell focus catalyst carrier and organic macromolecule
Material.Be conducive to improve the mass transfer ability of material in the catalyst in catalyst carrier material application, it is living so as to improve catalyst
Property and selectivity.
Aluminium hydroxide is added in rubber or alumina ratio is more typical, for example, CN103102686A provides a kind of hydrogen-oxygen
Change aluminium-silicon rubber composite material preparation method, it is characterized in that: it is carrier by filler, silicon rubber of aluminium hydroxide, in direct current
Compound heat-conducting silicon rubber is prepared off field.The blending ratio of aluminium hydroxide and silicon rubber is 0:100-40:60.In external dc
The composite heat-conducting silicon rubber prepared under current field condition, can be improved effective thermal conductivity 30%.CN1130416C discloses a kind of oxidation
Diene rubber composition of the aluminium as reinforcing filler and tire and tire tread comprising the composition.With at least one diene
Rubber composition based on olefin elastomer, including aluminium oxide and coupling agent as reinforcing filler, the aluminium oxide include
BET specific surface area is 30-400m2g-1, average particle size is less than or equal to 500nm, a high proportion of Al-OH surface reaction activity function
Group and polymolecularity, the amount of coupling agent are every square metre of aluminium oxide 10-7-10-5Mol, the composition are particularly suitable for manufacture tire.
CN1760274A is related to the silicone rubber compound for high voltage insulator.More precisely, it is related to addition or peroxide crosslinking
Silicone rubber compound, for the composition using aluminium hydroxide as filler, used aluminium hydroxide is the hydrogen-oxygen of unprocessed mistake
Change aluminium.
In conclusion macroporous aluminium oxide has been successfully applied to multiple catalyst systems, to the activity of catalyst, selectivity and
There is different degrees of improvement result in terms of stability.Hard mould agent although available preferable macroporous structure, but adjusting
Saving pore size aspect, there are certain deficiencies；And the solubility of polyvinyl alcohol soft template in water is by the shadow of its degree of polymerization
It rings, it is caused to be restricted when being used to prepare super large porous aluminum oxide.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst for selectively hydrodesulfurizing containing macropore alumina supporter, the catalysis
Agent, as template, synthesizes that aperture size is adjustable using macromolecule SBR emulsion, and the macropore oxygen that macropore ratio is easily-controllable
Change alumina supporter, and prepared by carried metal active component, can be used for catalytic gasoline selective hydrodesulfurizationmodification.
The technical problem to be solved by the present invention is to improve the activity and selectivities of existing Hydrobon catalyst, especially suitable
The hydrofinishing for closing the high Olefinic catalytic cracking gasoline of high-sulfur, mainly solves existing Catalytic Cracking Gasoline Selective Hydrodesulfurization Technology
Present in desulfurization degree is low, desulfuration selectivity is poor and loss of octane number is big problem.
In order to solve the above technical problems, the invention discloses a kind of selective hydrodesulfurizations containing macropore alumina supporter to urge
Agent, by weight percentage, the alumina support containing macropore are 82-95wt%, preferably 75-90wt%, and oxidation molybdenum content is
2-14wt%, preferably 5-12wt%, cobalt oxide content 1-5wt%, preferably 1-3wt%.
Catalyst disclosed by the invention is using conventional dipping method preparation, it can is co-impregnation, is also possible to point
Infusion process is walked, the present invention is using following preparation method: the soluble-salt containing molybdenum and containing cobalt being configured to maceration extract at normal temperature, soaked
Alumina support of the stain containing macropore, then room temperature is aged 2-5h, then in 80-150 DEG C of dry 2-8h, 450-600 DEG C of roasting 3-
10h is to get finished catalyst.
Auxiliary agent potassium can also be added in above-mentioned Hydrobon catalyst, and in terms of catalyst weight percent, potassium oxide content is
0.1-3.0wt%.
A kind of alumina support containing macropore provided by the present invention, the pore-size distribution 60-400nm of the alumina support,
It is preferred that 60~200nm, more preferable 80-180nm, macropore ratio 2-70%, preferably 10-70%, Kong Rong 0.8-2.2mL/g, preferably
0.8-1.2mL/g or preferred 1.8-2.2mL/g, carrier inside duct have connectivity.The alumina support uses macromolecule fourth
Benzene rubber latex is as expanding agent, and alumina support is more prone to produce macropore, and pore-size distribution is more concentrated, in 60-
400nm。
Alumina support provided by the invention containing macropore, aperture can by adjusting the molecular weight of expanding agent, partial size with
And additional amount is realized.Pore-size distribution can change between 60-400nm, such as 60-90nm, 140-180nm, 240-300nm etc.
Range.Macropore ratio is 0.1-70%, can be tuned as the ranges such as 10-70%.
The present invention also provides a kind of preparation methods containing macropore alumina supporter, first by boehmite powder and sesbania
Powder is added in kneader and is uniformly mixed；Then partial size is prepared in the SBR emulsion of 10-500nm, by organic acid or inorganic
Acid is added thereto, and sour additional amount is the 2-8wt% of boehmite；Subsequently the acid solution containing SBR emulsion is added
Enter into boehmite powder to mediate uniformly, the additional amount of the acid solution containing SBR emulsion is the 0.1- of boehmite
45wt%, preferably 0.5-30wt%, more preferable 5-20wt% most obtain the oxygen containing macropore through extrusion-molding-drying-roasting afterwards
Change alumina supporter.
The expanding agent SBR emulsion the preparation method is as follows: by polymer grade styrene monomer, polymer grade fourth two
Paradigmatic system is added in alkene monomer, deionized water, emulsifier, electrolyte and adjuvant, total with styrene and two kinds of monomers of butadiene
Quality is 100 parts of meters, and wherein styrene dosage is 10-40 parts, preferably 20-35 parts；Deionized water dosage is 100-300 parts；Cream
Agent dosage is 2-10 parts；Electrolyte dosage is 0.5-2 parts；Adjuvant dosage is 0.01-0.2 parts.Under agitation, make
Material mixing pre-emulsification 20-40min is stated into emulsion, initiator and regulator are added after being cooled to 5-8 DEG C, with styrene and fourth
Two kinds of monomer gross mass of diene are 100 parts of meters, and initiator amount is 0.01-0.5 parts, and regulator dosage is 0.5-2 parts；Control temperature
5-8 DEG C, pressure 0.1-0.3MPa, reaction time 7-10h of degree, is added terminator when two kinds of monomer conversions reach 60-70%
Polymerization reaction is terminated, SBR emulsion is obtained.
The partial size of the SBR emulsion of synthesis is in 10-500nm, and partial size is mainly by the type of emulsifier, dosage and adjusting
Agent dosage is controlled, in general, in synthesis process select emulsifier emulsifying effectiveness is better, dosage is more and regulator
Dosage is more, and the partial size for synthesizing rubber latex will be smaller.
Emulsifier of the present invention be selected from nonionic emulsifier (such as sorbitan ester, TWEEN Series, this Pan series,
It is preferred that sorbitan ester), amphoteric emulsifier (such as carboxylic acids, sulfuric acid ester, phosphoric acid ester) and macromolecule emulsifier (such as carboxylic first
One or more of base cellulose, p styrene sulfonic acid salt etc.), electrolyte is selected from potassium chloride, sodium chloride, sodium bisulfate and fluorine
Change one or more of sodium, preferably potassium chloride, adjuvant include chelating agent (ethylenediamine tetra-acetic acid and its metal salt, preferably second
Ethylenediamine tetraacetic acid (EDTA) ferrisodium salt (EDTA)), pH adjusting agent (KOH, Na2CO3Deng) and surface tension modifier (amylalcohol, hexanol etc.)
One or more of, organic peroxide (the different phenylpropyl alcohol of peroxidating two, dibenzoyl peroxide), oxygen may be selected in the initiator
Change-reduction system (potassium peroxydisulfate-ferrous iron salt system, preferably sulfuric acid are ferrous), azo-initiator (azodiisobutyronitrile).It adjusts
Agent is also referred to as chain-transferring agent, for the compound containing sulphur, nitrogen, phosphorus and organic unsaturated bond, preferably mercaptan, thiuram-disulfide.Institute
Stating terminator may be selected hydroquinone type, quinones, nitroso, sulfur-containing compound.
The additional amount of acid solution containing SBR emulsion is the 0.1-45wt% of boehmite, and sour additional amount is quasi-
The 2-8wt% of boehmite, preferably 3-5wt%, the acid used are in the art common various organic acids or inorganic acid, can be with
For acetic acid, citric acid, nitric acid and hydrochloric acid etc..The source of the boehmite powder and property are without restriction, Ke Yiwei
The product of the techniques such as carbonizatin method, nitrate method, sulfuric acid process, ammonium method production.It is adapted to different range specific surface area, Kong Rong, aperture
Boehmite.
Kneading and extrusion technique containing macropore alumina supporter are as follows: be slowly added into the configured acid solution containing expanding agent
In the sesbania powder and boehmite mixed powder mixed in advance, extrusion, molding are carried out after mediating uniformly, by 80-200
DEG C drying 2-8h, 550-700 DEG C of roasting 4-6h finally obtain the alumina support containing macropore.
In order to which macropore alumina supporter has better performance, catalytic gasoline selective is applied to as carrier and adds hydrogen
Auxiliary agent boron, potassium, strontium are preferably introduced in desulphurization catalyst, in alumina support, detailed process includes the following steps: to intend first thin
Diaspore powder and sesbania powder are added in kneader and are uniformly mixed；Then the water-soluble of boronic acid containing, potassium nitrate and strontium nitrate is added
Liquid, and partial size is prepared in the SBR emulsion of 10-500nm, organic acid or inorganic acid are added thereto, sour additional amount is quasi-
The 2-8wt% of boehmite；Subsequently the acid solution containing SBR emulsion is added in boehmite powder and is mediated
Uniformly, the additional amount of the acid solution containing SBR emulsion is 0.1-45wt%, the preferably 0.5-30wt% of boehmite, more
It is preferred that 5-20wt%, most obtains the modified macroporous aluminium oxide of used additives boron, potassium and strontium and carries through extrusion-molding-drying-roasting afterwards
Body.The composition of carrier is with oxidation material meter: the aluminium oxide including 93-99.5wt%, the boron oxide of 0.1-2.5wt%, 0.1-
The potassium oxide of 4.5wt%, the strontium oxide strontia of 0.1-4.5wt%.
By the modification of auxiliary agent boron, potassium, strontium, which is prepared into catalyst for selectively hydrodesulfurizing, such as the catalysis of cobalt molybdenum
Agent is conducive to adjust its acidity, reduces the polymerization of alkene in feedstock oil, inhibits catalytic inner coking deactivation, and carbon deposition rate is low, from
And improve the stabilized hydrogenation of catalyst.
The macropore alumina supporter modified by auxiliary agent boron, potassium, strontium of the present invention, can further change it
Into being surface modified preferably by potassium and strontium to the carrier of boron containing auxiliary agent, potassium, strontium, detailed process includes the following steps: to configure
Containing potassium nitrate and strontium nitrate aqueous solution as maceration extract impregnated carrier, used additives potassium is obtained through drying, roasting and strontium carries out surface
The complex carrier of modification.Complex carrier surface oxidation potassium and oxidation content of strontium are controlled respectively in 0.1-4.5wt% and 0.1-
In the range of 4.5wt%.
Macropore alumina supporter surface provided by the invention through potassium and strontium modification after, make its surface potassium and strontium concentration with
The content of the concentration of carrier inside potassium and strontium formation concentration difference, carrier surface potassium and strontium is higher than the content of carrier inside potassium and strontium,
That is the molar content or mass content of carrier surface potassium oxide and strontium oxide strontia can be the content of internal oxidation potassium and strontium oxide strontia
2.1-3.0 again.Carrier surface can be made to tend to equally distributed state in this way, reduce the acidity of carrier surface.Using the carrier
It is prepared into catalyst for selectively hydrodesulfurizing, can be improved the specific surface area of catalyst, inhibits its surface coking deactivation, raising is urged
The dispersibility and adhesion on carrier such as agent active component cobalt molybdenum, active component cobalt, molybdenum etc. not easily run off, and effectively solve in this way
Active decline problem caused by having determined because of the loss such as active component cobalt, molybdenum.Carrier surface potassium oxide and strontium oxide strontia mole contain
Amount or mass content are preferably 2.1-3.0 times of internal oxidation potassium and oxidation content of strontium, and adjusting carrier surface is not achieved lower than 2 times
Acidity improves dispersion degree and adhesion of the active component on carrier, the purpose that inhibitory activity component is lost.
Catalyst for selectively hydrodesulfurizing provided by the invention, performance evaluation is reactor used to can be fixed bed adiabatic
Reactor is also possible to fixed bed isothermal reactor, preferably fixed bed adiabatic reactor.
Compared with prior art, the present invention is without being added the reagents such as coagulant, dispersing agent, chelating agent, and preparation cost is significantly
It reduces.The SBR emulsion of synthesis can make its molecular weight from thousand grades to ten by control synthesis condition and regulator dosage
Ten thousand grades are adjustable, and the type and dosage of coordinated control emulsifier are adjusted the partial size of SBR emulsion in 20-400nm, into
And the aperture of aluminium oxide can be controlled according to SBR emulsion partial size difference.
Expanding agent SBR emulsion is different from other polymers microballoon in the prior art, such as polystyrene microsphere,
SBR emulsion dissolubility is good, so that carrier inside duct has connectivity, rather than blind bore structure.The aluminium oxide of preparation
Carrier contains macroporous structure, while also containing meso-hole structure, and macropore range is in 3-50nm, mesoporous ratio 20-75%, preferably 20-
55%, it is a kind of containing Jie-macropore alumina support, and aperture is not uniform.
Detailed description of the invention
Fig. 1 is the graph of pore diameter distribution of the alumina support containing macropore prepared by embodiment 1.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
The specific surface area and mesoporous pore size of alumina support of the present invention containing macropore are produced using Merck & Co., Inc, the U.S.
3000 type automatic adsorption device of TStar II tested.The pore volume and pore-size distribution of alumina support containing macropore are adopted
It is tested with the full-automatic mercury injection apparatus of AutoPore IV9520 type that Merck & Co., Inc, the U.S. produces.
The sulfur content of full fraction FCC gasoline raw material of the present invention and reaction product uses TSN-2000 type sulphur apparatus for nitrogen examination
It is analyzed.FCC gasoline raw material and the research octane number (RON) of reaction product are tested using octane number testing machine.FCC gasoline raw material
And the composition of reaction product is analyzed using Agilent 7890B type gas chromatograph, data processing is by HW-2000PONA points
Dedicated chromatographic work station is analysed to complete.
In embodiments, the composition content such as the cobalt oxide of catalyst, molybdenum oxide is measured with x-ray fluorescence method (referring to " stone
Oily chemical analysis method (RIPP experimental method) ", Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes).
Embodiment 1
25 parts of (mass ratio) styrene, 75 parts of butadiene, 200 parts of deionized waters, 3.0 parts of creams are added in 10L polymeric kettle
Agent sorbitan ester, 1.5 parts of electrolyte KCl, 0.09 part of chelating agent iron edta sodium salt (EDTA), pre-emulsification
20min, addition 0.04 part of di-isopropylbenzene hydroperoxide of initiator and 0.04 part of ferrous sulfate after temperature is cooled to 5 DEG C, 0.20
Part regulator tert-dodecyl mercaptan, reacts 7h at 5 DEG C, and thiol terminations are added 60% or so in two kinds of monomer conversions controls
Agent obtains the SBR emulsion of partial size about 200nm.
The nitric acid that 12.0g concentration is 68% is add to deionized water mixing by the deionized water that 250mL is weighed with beaker
Uniformly, it is placed in 80 DEG C of water-bath.It weighs 9.0g SBR emulsion and is added to prepared deionized water nitric acid solution
In, it stirs evenly, obtains the acid solution containing expanding agent.It weighs 300g boehmite powder and 15g sesbania powder is uniformly mixed, by butylbenzene
The acid solution of rubber is added in above-mentioned mixed powder, is clover shape through kneading-extruded moulding.It is 8 hours dry at 120 DEG C,
650 DEG C roast 4 hours, obtain the alumina support A-1 containing macropore.Alumina support specific surface area and pore-size distribution containing macropore
It is shown in Table 1.Fig. 1 is the graph of pore diameter distribution of the alumina support A-1 containing macropore.As shown in Figure 1, the alumina support of preparation has double
The structure of peak pore size distribution.
It takes 13.00g ammonium heptamolybdate, 13.21g cobalt acetate to be added in 70mL distilled water, is made into maceration extract impregnated carrier, obtains
The catalyst precursor arrived is aged 4h in room temperature, and 130 DEG C of dry 6h, 590 DEG C of roasting 5h obtain catalyst 1.Catalyst 1 is main
Composition: cobalt oxide 3wt%, molybdenum oxide 8wt%, carrier 89wt%.
Embodiment 2
30 parts of (mass ratio) styrene, 70 parts of butadiene, 200 parts of deionized waters, 4.0 parts of creams are added in 10L polymeric kettle
Agent sorbitan ester, 1.0 parts of electrolyte KCl, 0.12 part of chelating agent iron edta sodium salt (EDTA), pre-emulsification
30min, addition 0.04 part of di-isopropylbenzene hydroperoxide of initiator and 0.04 part of ferrous sulfate after temperature is cooled to 5 DEG C, 0.40
Part regulator tert-dodecyl mercaptan, reacts 7h at 5 DEG C, and hydroquinone type is added 60% or so in two kinds of monomer conversions controls
Terminator obtains the SBR emulsion of partial size about 100nm.
The deionized water that 260mL is weighed with beaker, 15.0g acetic acid is add to deionized water uniformly mixed, is placed in 80
DEG C water-bath in.It weighs 15.0g SBR emulsion and is added in prepared deionized water acid solution, stir evenly,
Obtain the acid solution containing expanding agent.It weighs 300g boehmite powder and 15g sesbania powder is uniformly mixed, the acid solution of butadiene-styrene rubber is added
Enter into above-mentioned mixed powder, is clover shape through kneading-extruded moulding.6 hours dry at 150 DEG C, 600 DEG C of roastings 5 are small
When, obtain the alumina support A-2 containing macropore.Alumina support specific surface area and pore-size distribution containing macropore are shown in Table 1.
Ammonium heptamolybdate, cobalt acetate are added in distilled water, are made into maceration extract impregnated carrier, obtained catalyst precursor exists
Room temperature is aged 3h, and 120 DEG C of dry 7h, 550 DEG C of roasting 7h obtain catalyst 2.Catalyst 2 mainly forms: cobalt oxide 4.5wt%,
Molybdenum oxide 6wt%, carrier 89.5wt%.
Embodiment 3
35 parts of (mass ratio) styrene of addition in 10L polymeric kettle, 65 parts of butadiene, 200 parts of deionized waters, 5.0 part ten
Two acyl diglycollic amides, 0.8 part of electrolyte KCl, 0.10 part of pH adjusting agent KOH, pre-emulsification 20min are cooled to 7 DEG C to temperature
0.05 part of initiator azodiisobutyronitrile is added afterwards, 0.60 part of regulator tert-dodecyl mercaptan reacts 7h, two kinds of lists at 7 DEG C
Thiol terminations agent is added 60% or so in transformation rate control, obtains the SBR emulsion of partial size about 50nm.
The deionized water that 260mL is weighed with beaker, 18.0g acetic acid is add to deionized water uniformly mixed, is placed in 80
DEG C water-bath in.It weighs 120.0g SBR emulsion and is added in prepared deionized water acid solution, stir evenly,
Obtain the acid solution containing expanding agent.It weighs 300g boehmite powder and 15g sesbania powder is uniformly mixed, the acid solution of butadiene-styrene rubber is added
Enter into above-mentioned mixed powder, is clover shape through kneading-extruded moulding.8 hours dry at 130 DEG C, 700 DEG C of roastings 4 are small
When, obtain the alumina support A-3 containing macropore.Alumina support specific surface area and pore-size distribution containing macropore are shown in Table 1.
Ammonium heptamolybdate, cobalt nitrate are added in distilled water, are made into maceration extract impregnated carrier, obtained catalyst precursor exists
Room temperature is aged 5h, and 120 DEG C of dry 5h, 600 DEG C of roasting 5h obtain catalyst 3.Catalyst 3 mainly forms: cobalt oxide 2wt%, oxygen
Change molybdenum 12.5wt%, carrier 85.5wt%.
Embodiment 4
28 parts of (mass ratio) styrene, 72 parts of butadiene, 200 parts of deionized waters, 2.0 parts of mistakes are added in 10L polymeric kettle
Water sorbitol ester, 1.2 parts of electrolyte KCl, 0.13 part of chelating agent iron edta sodium salt (EDTA), pre-emulsification 20min, to
0.04 part of peroxidating bis-isobutyronitrile of initiator, 0.15 part of regulator tert-dodecyl mercaptan, at 5 DEG C is added after being cooled to 7 DEG C in temperature
Lower reaction 7h, two kinds of monomer conversion controls are added thiol terminations agent 60% or so, obtain the butadiene-styrene rubber of partial size about 300nm
Lotion.
10.0g concentration is that 68% nitric acid is add to deionized water mixing by the deionized water that 250mL is weighed with beaker
It is even, it is placed in 80 DEG C of water-bath.It weighs 16.0g SBR emulsion and is added in prepared deionized water acid solution,
It stirs evenly, obtains the acid solution containing expanding agent.It weighs 300g boehmite powder and 15g sesbania powder is uniformly mixed, by butylbenzene rubber
The acid solution of glue is added in above-mentioned mixed powder, is clover shape through kneading-extruded moulding.It is 8 hours dry at 130 DEG C, 600
DEG C roasting 6 hours, obtain the alumina support A-4 containing macropore.Alumina support specific surface area containing macropore is shown in pore-size distribution
Table 1.
Ammonium heptamolybdate, cobalt acetate are added in distilled water, are made into maceration extract impregnated carrier, obtained catalyst precursor exists
Room temperature is aged 4h, and 130 DEG C of dry 4h, 600 DEG C of roasting 6h obtain catalyst 4.Catalyst 4 mainly forms: cobalt oxide 2.5wt%,
Molybdenum oxide 9.5wt%, carrier 88wt%.
Comparative example 1
It weighs 300g boehmite powder and 15g sesbania powder is uniformly mixed, the deionized water of 250mL is measured with beaker, it will
The nitric acid that 12.0g concentration is 68% is add to deionized water uniformly mixed, is then added to boehmite and sesbania powder
It is clover shape through kneading-extruded moulding in mixed powder.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, are contained
The alumina support D-1 of macropore.Alumina support specific surface area and pore-size distribution containing macropore are shown in Table 1.Comparative example 1 and embodiment
1 difference is not add expanding agent.
It takes 13.00g ammonium heptamolybdate, 13.21g cobalt acetate to be added in 70mL distilled water, is made into maceration extract impregnated carrier, obtains
The catalyst precursor arrived is aged 4h in room temperature, and 130 DEG C of dry 6h, 590 DEG C of roasting 5h obtain comparative catalyst D-1.Comparison is urged
Agent D-1 is mainly formed: cobalt oxide 3wt%, molybdenum oxide 8wt%, carrier 89wt%.
Embodiment 5
25 parts of (mass ratio) styrene, 75 parts of butadiene, 200 parts of deionized waters, 3.0 parts of creams are added in 10L polymeric kettle
Agent sorbitan ester, 1.5 parts of electrolyte KCl, 0.09 part of chelating agent iron edta sodium salt (EDTA), pre-emulsification
20min, addition 0.04 part of di-isopropylbenzene hydroperoxide of initiator and 0.04 part of ferrous sulfate after temperature is cooled to 5 DEG C, 0.20
Part regulator tert-dodecyl mercaptan, reacts 7h at 5 DEG C, and thiol terminations are added 60% or so in two kinds of monomer conversions controls
Agent obtains the SBR emulsion of partial size about 200nm.
The nitric acid that 12.0g concentration is 68% is add to deionized water mixing by the deionized water that 250mL is weighed with beaker
Uniformly, it is placed in 80 DEG C of water-bath.It weighs 9.0g SBR emulsion and is added to prepared deionized water nitric acid solution
In, it stirs evenly, obtains the acid solution containing expanding agent.It weighs 300g boehmite powder and 15g sesbania powder is uniformly mixed, by butylbenzene
The acid solution of rubber is added in above-mentioned mixed powder, is clover shape through kneading-extruded moulding.It is 8 hours dry at 120 DEG C,
650 DEG C roast 4 hours, obtain the alumina support A-1 containing macropore.
It takes 13.00g ammonium heptamolybdate, 13.21g cobalt acetate, 4.27g potassium nitrate to be added in 70mL distilled water, is made into dipping
Liquid impregnated carrier, obtained catalyst precursor are aged 4h in room temperature, and 130 DEG C of dry 6h, 590 DEG C of roasting 5h obtain catalyst
5.Catalyst 5 mainly forms: cobalt oxide 3wt%, molybdenum oxide 8wt%, potassium oxide 1.5wt%, carrier 87.5wt%.
Embodiment 6
25 parts of (mass ratio) styrene, 75 parts of butadiene, 200 parts of deionized waters, 3.0 parts of creams are added in 10L polymeric kettle
Agent sorbitan ester, 1.5 parts of electrolyte KCl, 0.09 part of chelating agent iron edta sodium salt (EDTA), pre-emulsification
20min, addition 0.04 part of di-isopropylbenzene hydroperoxide of initiator and 0.04 part of ferrous sulfate after temperature is cooled to 5 DEG C, 0.20
Part regulator tert-dodecyl mercaptan, reacts 7h at 5 DEG C, and thiol terminations are added 60% or so in two kinds of monomer conversions controls
Agent obtains the SBR emulsion of partial size about 200nm.
12.0g concentration is that 68% nitric acid is add to deionized water mixing by the deionized water that 250mL is weighed with beaker
It is even, it is placed in 80 DEG C of water-bath.It weighs 9.0g SBR emulsion and is added in prepared deionized water nitric acid solution,
It stirs evenly, obtains the acid solution containing expanding agent.It weighs 300g boehmite powder and 15g sesbania powder is uniformly mixed, then claim respectively
Boric acid 2.23g, potassium nitrate 2.08g are taken, strontium nitrate 1.67g is dissolved completely in the water that boracic, potassium and strontium are made into 60mL distilled water
Solution.Above-mentioned aqueous solution is added in boehmite powder and the mixture of sesbania powder, then again by the acid solution of butadiene-styrene rubber
It is added thereto, is clover shape through kneading-extruded moulding.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, obtain with helping
The modified alumina support A-6 containing macropore of agent boron, potassium and strontium.
Ammonium heptamolybdate, cobalt nitrate are added in distilled water, maceration extract impregnated carrier A-6, body before obtained catalyst are made into
Body is aged 4h in room temperature, and 110 DEG C of dry 3h, 550 DEG C of roasting 4h obtain catalyst C-1.Catalyst C-1 is mainly formed: cobalt oxide
3wt%, molybdenum oxide 7wt%, carrier 90wt%.
Embodiment 7
25 parts of (mass ratio) styrene, 75 parts of butadiene, 200 parts of deionized waters, 3.0 parts of creams are added in 10L polymeric kettle
Agent sorbitan ester, 1.5 parts of electrolyte KCl, 0.09 part of chelating agent iron edta sodium salt (EDTA), pre-emulsification
20min, addition 0.04 part of di-isopropylbenzene hydroperoxide of initiator and 0.04 part of ferrous sulfate after temperature is cooled to 5 DEG C, 0.20
Part regulator tert-dodecyl mercaptan, reacts 7h at 5 DEG C, and thiol terminations are added 60% or so in two kinds of monomer conversions controls
Agent obtains the SBR emulsion of partial size about 200nm.
12.0g concentration is that 68% nitric acid is add to deionized water mixing by the deionized water that 250mL is weighed with beaker
It is even, it is placed in 80 DEG C of water-bath.It weighs 9.0g SBR emulsion and is added in prepared deionized water nitric acid solution,
It stirs evenly, obtains the acid solution containing expanding agent.It weighs 300g boehmite powder and 15g sesbania powder is uniformly mixed, then claim respectively
Boric acid 2.23g, potassium nitrate 2.08g are taken, strontium nitrate 1.67g is dissolved completely in the water that boracic, potassium and strontium are made into 60mL distilled water
Solution.Above-mentioned aqueous solution is added in boehmite powder and the mixture of sesbania powder, then again by the acid solution of butadiene-styrene rubber
It is added thereto, is clover shape through kneading-extruded moulding.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, obtain with helping
The modified alumina support A-6 containing macropore of agent boron, potassium and strontium.
The macropore alumina supporter A-6 that used additives boron, potassium and strontium were modified is surface modified again using potassium and strontium,
Detailed process includes the following steps: potassium nitrate and strontium nitrate being made into maceration extract, weighs potassium nitrate 4.83g, strontium nitrate respectively
3.84g is dissolved completely in 30mL distilled water, is then made into maceration extract oxide impregnation alumina supporter A-6 with deionized water dilution, is passed through
Dry, roasting obtains the alumina composite carrier A-7 with potassium and strontium surface modification.
Ammonium heptamolybdate, cobalt acetate are added in distilled water, are made into maceration extract impregnated carrier, obtained catalyst precursor exists
Room temperature is aged 2h, and 150 DEG C of dry 5h, 500 DEG C of roasting 9h obtain catalyst C-2.Catalyst C-2 is mainly formed: cobalt oxide
1.5wt%, molybdenum oxide 13wt%, alumina composite carrier 85.5wt%.
Performance evaluation, evaluation result are as follows: catalyst C-1 and C- are carried out to catalyst for selectively hydrodesulfurizing C-1 and C-2
2 product desulfurization degrees are respectively 83.1% and 84.5%, and alkene drop amount is respectively 1.9% and 1.7%, and loss of octane number is respectively
0.6 unit and 0.5 unit.It is indicated above that using through prepared by the modified macropore alumina supporter of auxiliary agent boron, potassium, strontium
Catalyst for selectively hydrodesulfurizing can solve in the prior art that catalyst desulfurizing rate is low, desulfuration selectivity is poor and loss of octane number
Big problem.
Study on the stability, reaction operation 500h, catalyst C-1 are carried out to catalyst for selectively hydrodesulfurizing C-1 and C-2 again
It is respectively 81.6% and 83.8% with C-2 product desulfurization degree, loss of octane number is respectively 0.6 unit and 0.4 unit, carbon distribution
Rate 2.5 and 2.1, catalyst reaction performance are stablized, and active component not easily runs off, and carbon deposition rate is low, and it is steady to be indicated above its hydrodesulfurization
It is qualitative good.
1 macropore alumina supporter specific surface area of table and pore-size distribution
Performance evaluation is carried out to catalyst for selectively hydrodesulfurizing 1~5 and comparative catalyst D-1.Catalyst is packed into
In 10mL reactor, presulfurization processing is carried out to it, sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, concentration 1wt%；Sulphur
Change pressure is 2.8MPa, hydrogen to oil volume ratio 300:1, volume space velocity 2h-1, vulcanization program is respectively in 230 DEG C, 270 DEG C of sulphur
Change processing 6h.After to vulcanizing treatment, it is switched to catalytically cracked gasoline displacement 10h, adjusts reaction process condition are as follows: reactor
260 DEG C of temperature, reaction pressure 1.6MPa, volume space velocity 3h-1, hydrogen to oil volume ratio 250:1.Start sampling analysis after reaction about 50h.
Its evaluation result is as shown in table 2.
2 catalyst reaction performance evaluation result of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | |
| Desulfurization degree, % | 82.7 | 81.9 | 83.3 | 82.1 | 82.9 | 79.0 |
| Alkene drop amount, % | 1.8 | 2.5 | 2.2 | 1.7 | 1.6 | 5.2 |
| Loss of octane number | 0.5 | 0.8 | 0.6 | 0.5 | 0.4 | 2.3 |
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (13)
1. a kind of Hydrobon catalyst containing macropore alumina supporter, which is characterized in that with total catalyst weight percentages,
Alumina support of the catalyst containing macropore is 82-95wt%, and carrier uses SBR emulsion as expanding agent, aoxidizes molybdenum content
For 2-14wt%, cobalt oxide content 1-5wt%.
2. Hydrobon catalyst according to claim 1, which is characterized in that the oxidation molybdenum content is 5-12wt%,
Cobalt oxide content is 1-3wt%.
3. Hydrobon catalyst according to claim 1, which is characterized in that the catalyst further includes auxiliary agent potassium, with
Catalyst weight percent meter, potassium oxide content 0.1-3.0wt%.
4. Hydrobon catalyst according to claim 1, which is characterized in that the pore-size distribution 60 of the alumina support
~200nm, macropore ratio 2~70%, 0.8~2.2ml/g of Kong Rong.
5. Hydrobon catalyst according to claim 1, which is characterized in that the alumina support is simultaneously also containing Jie
Pore structure, macropore range is in 3~50nm, mesoporous ratio 20~75%.
6. Hydrobon catalyst according to claim 1, which is characterized in that the pore-size distribution 80 of the alumina support
~90nm or 140~180nm or 240~300nm.
7. Hydrobon catalyst according to claim 5, which is characterized in that the macropore ratio 10 of the alumina support
~70%, the Kong Rongwei 0.8~1.2ml/g or 1.8~2.2ml/g of alumina support, mesoporous ratio 20~55%.
8. Hydrobon catalyst according to claim 1, which is characterized in that introduce auxiliary agent in the alumina support
Boron, potassium, strontium, the composition of alumina support is with oxidation material meter: the aluminium oxide including 93-99wt%, the oxygen of 0.1-2.5wt%
Change boron, the potassium oxide of 0.1-4.5wt%, the strontium oxide strontia of 0.1-4.5wt%.
9. Hydrobon catalyst according to claim 8, which is characterized in that the alumina carrier surface potassium oxide and
The content of strontium oxide strontia is higher than the content of carrier inside potassium oxide and strontium oxide strontia.
10. Hydrobon catalyst according to claim 9, it is characterised in that the alumina carrier surface potassium oxide and
The mass content of strontium oxide strontia is 2.1-3.0 times of the content of carrier inside potassium oxide and strontium oxide strontia.
11. a kind of preparation method of Hydrobon catalyst described in claim 1, which is characterized in that preparation process is as follows: will
Soluble-salt containing molybdenum and containing cobalt is configured to maceration extract, impregnates the alumina support containing macropore, then room temperature ageing 2-5h, then
80-150 DEG C of dry 2-8h, 450-600 DEG C of roasting 3-10h is to get finished catalyst.
12. the preparation method of Hydrobon catalyst according to claim 11, which is characterized in that the oxygen containing macropore
The preparation method for changing alumina supporter includes the following steps: to mix firstly, boehmite powder and sesbania powder are added in kneader
It closes uniformly, then, prepares partial size and be added thereto in the SBR emulsion of 10-500nm, and by organic acid or inorganic acid, it is sour
Additional amount is 2~8wt% of boehmite；The acid solution containing SBR emulsion is subsequently added to boehmite powder
It is mediated in end and sesbania powder uniformly, the additional amount of the acid solution containing SBR emulsion is 0.1~45wt% of boehmite,
By extrusion-molding-drying-roasting, the alumina support containing macropore is obtained.
13. the preparation method of Hydrobon catalyst according to claim 11 or 12, which is characterized in that described to contain macropore
The preparation method of alumina support include the following steps: firstly, boehmite powder and sesbania powder are added to kneader
In be uniformly mixed, then be added boronic acid containing, potassium nitrate and strontium nitrate aqueous solution；Partial size is prepared in the butadiene-styrene rubber of 10-500nm
Lotion, and organic acid or inorganic acid are added thereto, sour additional amount is 2~8wt% of boehmite；To subsequently it contain
The acid solution of SBR emulsion, which is added in boehmite powder and sesbania powder, mediates uniformly, the acid containing SBR emulsion
The additional amount of liquid is that 0.1~45wt% of boehmite obtains used additives potassium and strontium by extrusion-molding-drying-roasting
The alumina support being modified；Be reconfigured containing potassium nitrate and strontium nitrate aqueous solution as maceration extract dipping used additives potassium and strontium into
The modified alumina support of row obtains the complex carrier that used additives potassium and strontium are surface modified through drying, roasting.
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| US11377601B2 (en) * | 2018-09-18 | 2022-07-05 | King Fahd University Of Petroleum And Minerals | Boron and/or carbon nanofiber modified alumina-supported molybdenum-cobalt catalysts useful in hydrodesulfurization |
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|---|---|---|---|---|
| CN101337186A (en) * | 2008-08-27 | 2009-01-07 | 云南大学 | Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone |
| CN103086381A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Porous silica microsphere preparation method |
| CN107081155A (en) * | 2017-06-02 | 2017-08-22 | 钦州学院 | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101337186A (en) * | 2008-08-27 | 2009-01-07 | 云南大学 | Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone |
| CN103086381A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Porous silica microsphere preparation method |
| CN107081155A (en) * | 2017-06-02 | 2017-08-22 | 钦州学院 | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11377601B2 (en) * | 2018-09-18 | 2022-07-05 | King Fahd University Of Petroleum And Minerals | Boron and/or carbon nanofiber modified alumina-supported molybdenum-cobalt catalysts useful in hydrodesulfurization |
| US11713422B2 (en) | 2018-09-18 | 2023-08-01 | King Fahd University Of Petroleum And Minerals | Method for removing sulfur from liquid fuel |
| US11970665B2 (en) | 2018-09-18 | 2024-04-30 | King Fahd University Of Petroleum And Minerals | Carbon nanofiber-based hydrodesulfurization catalyst with molybdenum oxide and cobalt oxide |
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