CN107303484A - The preparation method and hydrotreating catalyst of a kind of siliceous macropore alumina supporter - Google Patents
The preparation method and hydrotreating catalyst of a kind of siliceous macropore alumina supporter Download PDFInfo
- Publication number
- CN107303484A CN107303484A CN201610252534.2A CN201610252534A CN107303484A CN 107303484 A CN107303484 A CN 107303484A CN 201610252534 A CN201610252534 A CN 201610252534A CN 107303484 A CN107303484 A CN 107303484A
- Authority
- CN
- China
- Prior art keywords
- acid
- boehmite
- accordance
- hours
- siliceous
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 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 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 76
- 239000000843 powder Substances 0.000 claims abstract description 48
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 46
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000007598 dipping method Methods 0.000 claims abstract description 17
- 239000003292 glue Substances 0.000 claims abstract description 15
- 238000004898 kneading Methods 0.000 claims abstract description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000006229 carbon black Substances 0.000 claims description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 241001502050 Acis Species 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 235000010447 xylitol Nutrition 0.000 claims description 5
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 4
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 4
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000811 xylitol Substances 0.000 claims description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 4
- 229960002675 xylitol Drugs 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005360 mashing Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000000274 adsorptive effect Effects 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 19
- 238000001035 drying Methods 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- AWLUSOLTCFEHNE-UHFFFAOYSA-N sodium;urea Chemical compound [Na].NC(N)=O AWLUSOLTCFEHNE-UHFFFAOYSA-N 0.000 description 1
- -1 sorbierite Chemical compound 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention provides the preparation method and hydrotreating catalyst of a kind of siliceous macropore alumina supporter, and prepared by carrier include：（1）The material after boehmite dry glue powder, dipping is impregnated with the aqueous solution containing polyalcohol and/or glucide and carries out hydro-thermal charing process；（2）Carbon powder and step after carbon powder, dipping are impregnated with siliceous solution（1）Boehmite, extrusion aid, peptizing agent kneading are into plastic, and first then roasting is calcined in air atmosphere in a nitrogen atmosphere for extrusion, drying, dried material, and silica containing alumina support is made.The hydrotreating catalyst includes above-mentioned carrier and hydrogenation active component.With higher mechanical strength while alumina support prepared by this method has larger pore volume and an aperture, the carrier is applied to prepare the fields such as weight, residuum hydrogenating and metal-eliminating catalyst.
Description
Technical field
The invention belongs to field of hydrogenation, preparation method and one kind more particularly to a kind of siliceous macropore alumina supporter add
Hydrogen handles catalyst.
Background technology
At present, in the production process of mink cell focus HDM, because feedstock oil contains a certain amount of vanadium, sulphur, arsenic, nickel
Deng impurity, deposition is easily formed, so that the duct of blocking catalyst, causes catalyst activity to decline rapidly, in addition inactivation, influence
Commercial Application.Catalyst with larger pore volume and larger bore dia holds metal and holds coke formation by force, can slow down catalyst
The service cycle for inactivating, making catalyst extends.The pore structure of catalyst is determined by the carrier for constituting catalyst, therefore, prepares tool
The carrier for having larger pore volume and larger bore dia is to prepare residual oil, especially prepare the decompression residuum higher for tenor and add
The key of hydrogen catalyst for demetalation.
CN1160602A disclose a kind of macropore alumina supporter for being suitable as Hydrodemetalation catalyst carrier and its
Preparation method.The preparation method of the macropore alumina supporter includes boehmite dry glue powder to be mixed with water or the aqueous solution,
Plastic is kneaded into, obtained plastic is extruded into bar on banded extruder, dries and is calcined and obtain product, is characterized in,
Carbon powder is additionally added in above process as physics expanding agent and can occur chemical action with boehmite or aluminum oxide
The chemical enlargement agent of phosphorous, silicon or boron compound.Wherein carbon powder consumption is 3-10 weights %（On the basis of the weight of aluminum oxide）.
Obtained alumina support can be used for preparing mink cell focus particularly residuum hydrogenating and metal-eliminating and/or Hydrobon catalyst.
US4448896 proposes to be used as expanding agent using carbon black.Expanding agent is well mixed with boehmite dry glue powder, to
It is 4.3% aqueous solution of nitric acid kneading 30 minutes that mass fraction is added in said mixture, and it is 2.1% then to add mass fraction
Ammonia spirit kneading 25 minutes, extruded moulding after kneading is uniform, the fired obtained final alumina support of carrier after shaping.Its
The addition of middle carbon powder is preferably greater than the 20% of activated alumina or its precursor weight.
CN102441436A discloses a kind of preparation method of alumina support.The step of this method prepares alumina support is such as
Under：（1）Boehmite dry glue powder and extrusion aid are well mixed, then add and have dissolved physics expanding agent and chemical enlargement agent
The aqueous solution；（2）By step（1）Resulting material is well mixed, the extruded moulding on banded extruder；（3）By step（2）Resulting material is done
Final alumina support is made in dry, roasting.
In summary, prior art prepares usually used physics expanding agent and chemical enlargement during macropore alumina supporter
Agent improves the aperture of carrier, and the addition of expanding agent can make the increase of alumina support macropore content really.But in alumina support
Forming process, need to be by kneadings such as boehmite dry glue powder, extrusion aid, peptizing agents into plastic, then extruded moulding, due to squeezing
The presence of the larger pressure of bar process can make the macropore of alumina powder itself occur partly to cave in, so that the pore volume of final carrier
And macropore content is substantially reduced.In addition, the mechanical strength of alumina support prepared by existing method needs further raising.
The content of the invention
For existing technical deficiency, the present invention provides a kind of preparation method of siliceous macropore alumina supporter, this method
The alumina support of preparation is with higher mechanical strength while have larger pore volume and an aperture, and present invention simultaneously provides one kind
Hydrotreating catalyst, the catalyst is applied to prepare weight, residuum hydrogenating and metal-eliminating field.
The preparation method of the siliceous macropore alumina supporter of the present invention, including following process：
（1）The material impregnated with the aqueous solution containing polyalcohol and/or glucide after boehmite dry glue powder, dipping enters water-filling
Hot charing process；
（2）Carbon powder and step after carbon powder, dipping are impregnated with siliceous solution（1）Boehmite, extrusion aid, peptizing agent kneading
Into plastic, first then roasting is calcined in air atmosphere in a nitrogen atmosphere for extrusion, drying, dried material, is made and contains
The alumina support of silica.
In the inventive method, step（1）Described polyalcohol is in xylitol, sorbierite, mannitol or arabite
It is one or more of；Described carbohydrate is one or more of mixing in glucose, ribose or fructose etc.；Containing polyalcohol and/or sugar
The mass concentration of the aqueous solution of class material is 20%-40%.The consumption of the aqueous solution containing polyalcohol and/or glucide is that will intend thin
Diaspore dry glue powder is totally submerged, and dip time is 3-5 hours.
In the inventive method, step（1）Described hydro-thermal charing process is the heat treatment carried out in sealing device, preferably
Autoclave, can be dynamic response kettle or static reaction kettle, preferably static reaction kettle；Described hydro-thermal charing process temperature
For 120-160 DEG C, processing time is 8-16 hours.
In the inventive method, preferably by step（1）In boehmite pre-processed, preprocessing process is as follows：Will
Boehmite mixes mashing with deionized water, and the mixed acid solution of appropriate organic acid and inorganic acid is added into above-mentioned slurries,
The pH value for controlling slurries is 2-5, and progress is heated to reflux processing；Appropriate urea is added into above-mentioned slurries and carries out hydro-thermal process, water
Slurries after heat treatment are scrubbed, dry.
Wherein, described mixing pulping process is carried out using this area conventional method, boehmite and deionized water
Mass ratio is preferably 1:3-1:10；Described organic acid is one or more of mixing in acetic acid, oxalic acid or citric acid, described
Inorganic acid is one or more of mixing in sulfuric acid, nitric acid or hydrochloric acid；The material of organic acid and inorganic acid in mixed acid solution
Amount ratio be 1:3-1:6, the concentration of the mixed acid solution is calculated as 3-6mol/L with inorganic acid；It is described to be heated to reflux treatment temperature
For 30-60 DEG C, the time is heated to reflux for 1-5 hours；Described amount of urea and the mass ratio of boehmite are 1:5-1:10；
Borate is preferably added simultaneously while urea is added, and described borate can be metaborate, ortho-borate and many boron
One or more of mixing in hydrochlorate, the addition of borate counts the mass ratio with boehmite as 0.5 using boron oxide:100-
1.5:100；Described hydro-thermal process is the heat treatment under the self-generated pressure of autoclave, and treatment temperature is 120-160 DEG C,
Processing time is 4-8 hours；Described drying temperature is 100-120 DEG C, and drying time is 6-10 hours.
In the inventive method, step（2）Described siliceous solution is the ethanol solution containing esters of silicon acis, and wherein esters of silicon acis is selected from
One or more in methyl silicate, tetraethyl orthosilicate or butyl silicate.
In the inventive method, step（2）In described siliceous solution, silicone content is calculated as final vehicle weight with silica
2wt%-6wt%, the consumption of siliceous solution is the 30%-50% of carbon powder saturated water adsorptive value.
In the inventive method, step（2）The consumption of described carbon black powder is the 20%- of boehmite dry glue powder weight
40%。
In the inventive method, step（2）Described extrusion aid is one kind or several in sesbania powder, starch or methylcellulose
Plant, preferably sesbania powder, extrusion aid addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, step（2）Described peptizing agent is one kind or several in formic acid, acetic acid, citric acid or nitric acid
Mixing is planted, addition is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the inventive method, step（2）The drying condition is to be dried 1-10 hours at 100-130 DEG C.
In the inventive method, step（2）350-450 DEG C of sintering temperature under the nitrogen atmosphere, roasting time is that 4-6 is small
When, the sintering temperature under the air atmosphere is 450-550 DEG C, and roasting time is 4-8 hours.Process baked above is in tube furnace
Middle to carry out, before roasting, calcination atmosphere need to be full of whole tube furnace, and other can also be selected suitably to carry out baking operation
Equipment.
Present invention simultaneously provides a kind of hydrotreating catalyst, the catalyst includes hydrogenation active component and carrier, wherein
The carrier is siliceous macropore alumina supporter prepared by the inventive method.It can will be hydrogenated with and lived using technology well known in the art
Property component load on carrier, such as infusion process, the routine techniques such as kneading method.
Boehmite dry glue powder is through hydro-thermal charing process, and it is intercrystalline that the carbons material of formation is filled in boehmite
In duct, during extruded moulding, due to the presence of carbon particle, good supporting role can be played, the thin water of plan is effectively prevented
Caving in for aluminium stone macropore, improves the pore volume and macropore content of carrier.Silica and the oxygen on surface when being calcined under nitrogen atmosphere
Change aluminium effect, combine to form when being calcined under composite oxides, air atmosphere, carbon black powder oxidation is removed, and forms silica shell,
Due to the presence of silica, play the effect of good skeletal support, it is therefore prevented that macropore caves in, and corresponding duct is conducive to slag
The mass transfer of oil molecule and diffusion.In addition, silica is present, the acidity of carrier at corresponding macropore is reduced, improves and accordingly urges
The anti-carbon of agent and anti-caking power, making the service life of catalyst increases.The gas of carbon black powder oxidation thing formation can rise
To good reaming effect, the content of the carrier macropore of raising.
Preferred pair boehmite is pre-processed the inventive method simultaneously, and first boehmite is entered with mixed acid solution
Row processing, because mixed acid and boehmite act on more moderate, dissolves amorphous when can both overcome exclusive use organic acid
The halfway deficiency of phase hydrated alumina, can avoid damaging boehmite duct when inorganic acid is used alone again,
The dissolving of amorphous phase hydrated alumina is removed while boehmite pore structure is ensured.Aluminium salt after dissolving is retained in slurry
In liquid, then when adding urea into slurries and sealing hydro-thermal process, urea is decomposed into NH in high temperature environments3And CO2, NH3With
CO2NH is generated in the presence of water vapour4 +And HCO3 -Ion, NH4 +And HCO3 -Ion at high temperature under high pressure, makes the thin water of plan
Aluminium stone crystal grain is regrowed and crystallization, boehmite crystal grain is grown up, and is changed the accumulation mode of crystal grain, is improved macropore
Content, while dissolving Al3+Occurs following reaction：Al3++NH3.H2O Al(OH)3+NH4 +, Al (OH)3+ NH4 ++HCO3 -
NH4Al(OH)2CO3, NH4Al(OH)2CO3Gas is produced during roasting can play good reaming effect.Boron when adding borate
With aluminium salt double hydrolysis occur for hydrochlorate, and the boron oxide precipitating load of formation is in oxidation aluminium surface, while improving carrier aperture
The surface nature of modulation carrier.
Embodiment
The effect and effect of the inventive method are further illustrated with reference to embodiment, but is not limited to following implementation
Example.
Using N2Physics suction-desorption characterizes embodiment and comparative example carrier pore structure, and concrete operations are as follows：Using ASAP-
2420 type N2Physics is inhaled-is desorbed instrument and catalyst sample pore structure is characterized.Take a small amount of sample at 300 DEG C application of vacuum 3 ~
4 h, are finally placed in liquid nitrogen cryogenics by product（-200℃）Under the conditions of carry out nitrogen suction-desorption test.Wherein surface area is according to BET
Equation is obtained, and pore-size distribution and pore volume are obtained according to BJH models.
Embodiment and comparative example carrier components are characterized using XRF, concrete operations are as follows：Using Japanese RIGAKU companies ZSX-
100e type Xray fluorescence spectrometers, performance indications：X-ray tube Be window thickness：30μm；Power：4kW；Output voltage：20-60kV；
Output current：2-150mA；2 0.0001 ° of θ angles repeatabilities；2 0.0002 ° of θ angles accuracys.
Hydrogenation active component is loaded to the siliceous macroporous aluminium oxide of the inventive method preparation in embodiment using infusion process
On.Described hydrogenation active component maceration extract is to calculate to prepare according to final catalyst composition.In hydrogenation active component maceration extract,
Vib metals content is calculated as 7-15g/100ml with oxide, and group VIII tenor is calculated as 0.8-3g/ with oxide
100ml, can use volume impregnation, incipient impregnation or spray impregnating mode, and dip time is 1-5 hours.After dipping
Carrier through drying, roasting obtain hydrotreating catalyst.Wherein described drying condition is that 6-10 is dried at 80-120 DEG C
Hour；The roasting condition is to be calcined 3-6 hours at 400-600 DEG C.
Embodiment 1
Weigh boehmite（Shandong Aluminum Co., Ltd. Co., Ltd produces）200g is placed in beaker, and 400mL mass is added into beaker
Concentration impregnates 4 hours for 25% xylose alcohol solution.Material after dipping is through filtering, and filter cake is transferred in autoclave and carried out
Charing process, treatment temperature is 140 DEG C, and processing time is 10 hours.
Weigh 25 grams of carbon black powder be placed in spray rolling pot in, under rotary state, with atomizing type to rolling pot in carbon black powder
Unsaturation sprays the ethanol solution 7.5ml of the tetraethyl orthosilicate containing 2 grams of silica.Carbon black powder after dipping and 150 grams it is above-mentioned
Boehmite, 2g sesbania powders are sufficiently mixed, and the appropriate aqueous solution kneading dissolved with 2g acetic acid is added into above-mentioned material uniformly, is squeezed
Bar is molded.Wet stock after shaping is dried 8 hours in 110 DEG C.Dried material is placed in tube furnace, is passed through into tube furnace
Nitrogen makes nitrogen be full of whole burner hearth, is calcined 6 hours in 400 DEG C, then nitrogen leak is passed through air, is calcined 6 hours in 500 DEG C
Silicon-containing alumina carrier A1 is made, the property of carrier is shown in Table 1.
Embodiment 2
Be the same as Example 1, the mass ratio for being simply 40% with mass concentration is 1:1 sorbierite and the mixed aqueous solution of mannitol soak
Stain boehmite 3 hours.Charing process temperature is 130 DEG C, 14 hours processing times.The addition of carbon black powder is 20 grams, spray
The ethanol solution of that during leaching carbon black powder the is 7ml methyl silicate containing 3 grams of silica.Sintering temperature under nitrogen atmosphere is
350℃.Alumina support A2 of the present invention is made, the property of carrier is shown in Table 1.
Embodiment 3
Be the same as Example 1, the mass ratio for being simply 30% with mass concentration is 1:1 glucose and the mixed aqueous solution of ribose impregnate
Boehmite 5 hours.Charing process temperature is 120 DEG C, and the charing process time is 16 hours.The addition of carbon black powder is 35
Gram, the ethanol solution of that when spraying carbon black powder the is 14ml butyl silicate containing 5 grams of silica, the roasting under nitrogen atmosphere
Temperature is 450 DEG C.Alumina support A3 of the present invention is made, the property of carrier is shown in Table 1.
Embodiment 4
Be the same as Example 1, the mass ratio for being simply 20% with mass concentration is 1:1 arabite and the mixed aqueous solution of fructose
Impregnate boehmite 4 hours.Charing process temperature is 150 DEG C, and the charing process time is 12 hours.The addition of carbon black powder is
30 grams, the ethanol solution of that when spraying carbon black powder the is 13.5ml methyl silicate containing 4 grams of silica, under nitrogen atmosphere
Sintering temperature is 350 DEG C.Alumina support A4 of the present invention is made, the property of carrier is shown in Table 1.
Embodiment 5
Be the same as Example 1, simply impregnates boehmite 5 hours with mass concentration for 35% sorbitol aqueous solution.Charing process temperature
Spend for 160 DEG C, the charing process time is 8 hours.The addition of carbon black powder is 40 grams, and when spraying carbon black powder is that 25ml contains two
Sintering temperature under the ethanol solution for the tetraethyl orthosilicate that 6 grams of silica, nitrogen atmosphere is 450 DEG C.Aluminum oxide of the present invention is made
Carrier A5, the property of carrier is shown in Table 1.
Embodiment 6
Be the same as Example 1, is simply pre-processed, process is as follows to boehmite：Weigh 200g boehmite dry glue powders（Mountain
Eastern Aluminum Co., Ltd production）It is placed in round-bottomed flask, 600 grams of deionized water mashing is added into flask, into above-mentioned slurries
Appropriate nitric acid molar concentration is added for 3mol/L, acetic acid molar concentration is 1mol/L mixed acid solution, controls the pH value of slurries
3 and to be heated to reflux 3 hours in 40 DEG C.Above-mentioned slurries are transferred in autoclave, 20 grams of urea are added into mixed material and are incited somebody to action
Autoclave sealing is heat-treated 6 hours after 140 DEG C.It is cooled to after room temperature and filters mixed serum, washs, 120 DEG C of dryings 8 hours
Boehmite is made.
Weigh above-mentioned boehmite 200g to be placed in beaker, the xylose that 400mL mass concentrations are 25% is added into beaker
Alcohol solution impregnates 4 hours.Material after dipping is through filtering, and filter cake, which is transferred in autoclave, carries out charing process, processing temperature
Spend for 140 DEG C, processing time is 10 hours.Dry materials after processing.
Weigh 25 grams of carbon black powder be placed in spray rolling pot in, under rotary state, with atomizing type to rolling pot in carbon black powder
Unsaturation sprays the ethanol solution 7.5ml of the tetraethyl orthosilicate containing 2 grams of silica.Carbon black powder after dipping and 150 grams it is above-mentioned
Boehmite, 4g sesbania powders are sufficiently mixed, and the appropriate aqueous solution kneading dissolved with 5g acetic acid is added into above-mentioned material uniformly, is squeezed
Bar is molded.Wet stock after shaping is dried 8 hours in 110 DEG C.Dried material is placed in tube furnace, is passed through into tube furnace
Nitrogen makes nitrogen be full of whole burner hearth, is calcined 6 hours in 400 DEG C, then nitrogen leak is passed through air, is calcined 6 hours in 500 DEG C
Alumina support is made.
Weigh above-mentioned 100 grams of alumina support to be placed in beaker, add 150mlMo-Ni-NH3Solution（Contain
MoO312.0wt%, NiO3.0 wt%）Dipping 2 hours, filters off redundant solution, and 120 DEG C dry, then in 550 DEG C of roasting temperatures 5
Hour, catalyst C1 is made, the property of the catalyst is shown in Table 1.
Embodiment 7
Be the same as Example 6
Difference is：In preprocessing process, the addition of deionized water is 1400 grams.Mixed acid is dissolved with 4 mol sulfuric acid
With the mixed acid of 1mol oxalic acid, the pH value for controlling slurries is 2, and the temperature being heated to reflux is 30 DEG C, is flowed back 5 hours.Urea plus
It is 30 grams to enter amount, and hydro-thermal process temperature is 120 DEG C, hydro-thermal process 8 hours；
The mass ratio for being 40% with mass concentration is 1:1 sorbierite and the mixed aqueous solution dipping boehmite 3 of mannitol are small
When.Charing process temperature is 130 DEG C, 14 hours processing times；
The addition of carbon black powder is 20 grams, the ethanol of that when spraying carbon black powder the is 7ml methyl silicate containing 3 grams of silica
Solution；
Sintering temperature under nitrogen atmosphere is 350 DEG C, and catalyst C2 is made, and the property of the catalyst is shown in Table 1.
Embodiment 8
Be the same as Example 6
Difference is：In preprocessing process, simply the addition of deionized water is 2000 grams.Mixed acid is dissolved with 6mol/L
The mixed acid of sulfuric acid and 1mol/L citric acids, the pH value for controlling slurries is 5, is heated to reflux temperature for 60 DEG C, return time 1 is small
When.Urea addition is 40 grams, 160 DEG C of hydro-thermal process temperature, and hydrothermal conditions are 4 hours；
The mass ratio for being 30% with mass concentration is 1:1 glucose and the mixed aqueous solution dipping boehmite 5 of ribose are small
When.Charing process temperature is 120 DEG C, and the charing process time is 16 hours；
The addition of carbon black powder is 35 grams, the second of that when spraying carbon black powder the is 14ml butyl silicate containing 5 grams of silica
Alcoholic solution；
Sintering temperature under nitrogen atmosphere is 450 DEG C, and catalyst C3 is made, and the property of the catalyst is shown in Table 1.
Embodiment 9
Be the same as Example 6
Difference is：In preprocessing process, 3.0 grams of tetraboric acids are added into mixed material while simply adding urea
Sodium.
The mass ratio for being 20% with mass concentration is 1:1 arabite and the mixed aqueous solution dipping of fructose intend thin water
Aluminium stone 4 hours, charing process temperature is 150 DEG C, and the charing process time is 12 hours；
The addition of carbon black powder is 30 grams, that when spraying carbon black powder the is 13.5ml methyl silicate containing 4 grams of silica
Ethanol solution；
Sintering temperature under nitrogen atmosphere is 350 DEG C, and catalyst C4 is made, and the property of the catalyst is shown in Table 1.
Embodiment 10
Be the same as Example 6
Difference is：Simply boehmite is impregnated with mass concentration 5 hours for 35% sorbitol aqueous solution, at charing
It is 160 DEG C to manage temperature, and the charing process time is 8 hours；
The addition of carbon black powder is 40 grams, the second of that when spraying carbon black powder the is 25ml tetraethyl orthosilicate containing 6 grams of silica
Alcoholic solution；
Sintering temperature under nitrogen atmosphere is 450 DEG C, and catalyst C5 is made, and the property of the catalyst is shown in Table 1.
Comparative example 1
With example 1, simply esters of silicon acis is unsupported on carbon black powder, but is added when kneading, and comparative example aluminum oxide is made
Carrier A6, the property of carrier is shown in Table 1.
Comparative example 2
With example 1, comparative example alumina support is made in the simply addition in the form of kneading when carrier is molded by 25 grams of xylitols
A7, the property of carrier is shown in Table 1.
Comparative example 3
Be the same as Example 6, simply boehmite is not impregnated with xylitol and hydro-thermal process, but the xylitol of phase homogenous quantities is being carried
It is added to when body formed in the way of kneading in carrier, comparative example catalyst C6 is made, the property of catalyst is shown in Table 2.
Comparative example 4
Be the same as Example 6, simply esters of silicon acis is unsupported on carbon black powder, but is added when kneading, and comparative example catalysis is made
Agent C7, the property of catalyst is shown in Table 2.
The carrying alumina volume property of table 1.
The pore volume that pore size distribution refers to the diameter range endoporus of certain in carrier accounts for the percentage of total pore volume.
The catalyst property of table 2.
The pore volume that pore size distribution refers to the diameter range endoporus of certain in catalyst accounts for the percentage of total pore volume.
The result of table 1 shows that the macropore alumina supporter prepared using the inventive method is had while with larger aperture
There are larger pore volume, the pore size distribution of concentration, higher mechanical strength.Alumina support prepared by this method is applied to weight, residual oil
HDM field.
Hydrodemetalation catalyst will be prepared with above-mentioned A1-A7 carriers.Process is as follows：It is each that A1-A7 carriers are weighed respectively
100 grams, add 150mlMo-Ni-NH3Solution（Containing MoO312.0wt%, NiO3.0 wt%）Dipping 2 hours, filters off redundant solution,
120 DEG C of drying, then in 550 DEG C of roasting temperatures 5 hours, obtain Hydrodemetalation catalyst C8-C14.
Embodiment 11
Using feedstock oil listed by table 3 as raw material, C1-C14 catalytic performance, catalysis are evaluated on 200 milliliters of hydrogenation reaction device
Agent is long 2 ~ 3 millimeters bar, and catalyst loading amount is 100 milliliters, and reaction temperature is 375 DEG C, and hydrogen dividing potential drop is 13MPa, liquid hourly space velocity (LHSV)
For 1.0 hours-1, hydrogen to oil volume ratio is 1000, and reaction determines the content of each impurity in generation oil after 200 hours, calculate metal phase
To removal efficiency, evaluation result is shown in Table 3.
The raw material oil nature of table 3
The catalyst hydrogenation performance comparison of table 4
It can be seen from the data of table 4 compared with contrasting alumina support, the catalyst tool prepared by carrier of aluminum oxide of the present invention
There is higher HDM activity.
Claims (14)
1. a kind of preparation method of siliceous macropore alumina supporter, it is characterised in that including as follows：（1）With containing polyalcohol and/or
Material after the aqueous solution dipping boehmite dry glue powder of glucide, dipping carries out hydro-thermal charing process；（2）With siliceous molten
Carbon powder and step after immersion stain carbon powder, dipping（1）Boehmite, extrusion aid, peptizing agent kneading into plastic, extrusion,
First then roasting is calcined dry, dried material in air atmosphere in a nitrogen atmosphere, and silica containing oxidation is made
Alumina supporter.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described polyalcohol be xylitol, sorbierite,
One or more in mannitol or arabite；Described carbohydrate is that the one or more in glucose, ribose or fructose are mixed
Close；The mass concentration of the aqueous solution containing polyalcohol and/or glucide is 20%-40%；Water containing polyalcohol and/or glucide
Boehmite dry glue powder is is totally submerged by the consumption of solution, and dip time is 3-5 hours.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described hydro-thermal charing process is in sealing dress
The heat treatment of interior progress is put, described hydro-thermal charing process temperature is 120-160 DEG C, and processing time is 8-16 hours.
4. in accordance with the method for claim 1, it is characterised in that：By step（1）In boehmite pre-processed, in advance
Processing procedure is as follows：Boehmite is mixed into mashing with deionized water, appropriate organic acid is added into above-mentioned slurries and inorganic
The mixed acid solution of acid, the pH value for controlling slurries is 2-5, and progress is heated to reflux processing；Appropriate urea is added into above-mentioned slurries
Carry out the slurries after hydro-thermal process, hydro-thermal process scrubbed, dry.
5. in accordance with the method for claim 4, it is characterised in that：In preprocessing process, described organic acid is acetic acid, oxalic acid
Or one or more of mixing in citric acid, described inorganic acid is one or more of mixing in sulfuric acid, nitric acid or hydrochloric acid；It is mixed
The amount ratio for closing the material of organic acid and inorganic acid in acid solution is 1:3-1:6, the concentration of the mixed acid solution is with inorganic acid
It is calculated as 3-6mol/L；The treatment temperature that is heated to reflux is heated to reflux the time for 1-5 hours for 30-60 DEG C.
6. in accordance with the method for claim 4, it is characterised in that：In preprocessing process, described amount of urea is with intending thin water
The mass ratio of aluminium stone is 1:5-1:10.
7. in accordance with the method for claim 4, it is characterised in that：In preprocessing process, boron is added while urea is added
Hydrochlorate, described borate is one or more of mixing in metaborate, ortho-borate and multi-borate, the addition of borate
Amount counts the mass ratio with boehmite as 0.5 using boron oxide:100-1.5:100.
8. in accordance with the method for claim 4, it is characterised in that：In preprocessing process, described hydro-thermal process is in high pressure
Heat treatment under the self-generated pressure of reactor, treatment temperature is 120-160 DEG C, and processing time is 4-8 hours.
9. in accordance with the method for claim 1, it is characterised in that：Step（2）Described siliceous solution is the second containing esters of silicon acis
The one or more of alcoholic solution, wherein esters of silicon acis in methyl silicate, tetraethyl orthosilicate or butyl silicate.
10. in accordance with the method for claim 1, it is characterised in that：Step（2）In described siliceous solution, silicone content is with two
Silica is calculated as the 2wt%-6wt% of final vehicle weight, and the consumption of siliceous solution is the 30%-50% of carbon powder saturated water adsorptive value.
11. in accordance with the method for claim 1, it is characterised in that：Step（2）The consumption of described carbon black powder is the thin water aluminium of plan
The 20%-40% of stone dry glue powder weight.
12. in accordance with the method for claim 1, it is characterised in that：Step（2）Sintering temperature 350- under the nitrogen atmosphere
450 DEG C, roasting time is 4-6 hours.
13. in accordance with the method for claim 1, it is characterised in that：Step（2）Sintering temperature under the air atmosphere is
450-550 DEG C, roasting time is 4-8 hours.
14. a kind of hydrotreating catalyst, the catalyst includes hydrogenation active component and carrier, it is characterised in that：The carrier
The siliceous macropore alumina supporter prepared for claim 1 ~ 13 any claim methods described.
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