CN114749194B - Coal tar hydrogenation catalyst and preparation method thereof - Google Patents
Coal tar hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN114749194B CN114749194B CN202210024872.6A CN202210024872A CN114749194B CN 114749194 B CN114749194 B CN 114749194B CN 202210024872 A CN202210024872 A CN 202210024872A CN 114749194 B CN114749194 B CN 114749194B
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- CN
- China
- Prior art keywords
- coal tar
- hydrogenation catalyst
- water
- tar hydrogenation
- acid
- Prior art date
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- 239000011280 coal tar Substances 0.000 title claims abstract description 148
- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 57
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical group [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 83
- 229910052782 aluminium Inorganic materials 0.000 claims description 69
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 62
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 25
- 230000002378 acidificating effect Effects 0.000 claims description 25
- 229910052708 sodium Inorganic materials 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000007833 carbon precursor Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 8
- 229920000609 methyl cellulose Polymers 0.000 claims description 8
- 239000001923 methylcellulose Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 2
- 238000007493 shaping process Methods 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims 1
- 235000011162 ammonium carbonates Nutrition 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 235000010981 methylcellulose Nutrition 0.000 description 7
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229940024545 aluminum hydroxide Drugs 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- -1 cyclic aromatic hydrocarbon Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
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- 235000012239 silicon dioxide Nutrition 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
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- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J21/12—Silica and alumina
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C10G45/14—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 with moving solid particles
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Abstract
The invention provides a coal tar hydrogenation catalyst and a preparation method thereof, wherein the catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the carrier is a silicon-aluminum material, the active metal component is at least one of a VIB group metal and/or a VIII group metal, the preparation method comprises the steps of firstly mixing the silicon-aluminum material, a forming agent and a binder, then forming, drying and roasting to obtain the carrier, then introducing the active metal component to the carrier, and further drying and roasting to obtain the coal tar hydrogenation catalyst. The coal tar hydrogenation catalyst provided by the invention has the advantages of high active metal utilization rate, good wear resistance, strong water resistance, high impurity removal rate, high metal capacity, good cracking performance and the like, and is suitable for being applied to coal tar hydrogenation processes.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, relates to a catalytic material and a preparation method thereof, and particularly relates to a hydrogenation catalyst and a preparation method thereof.
Background
Coal tar is a liquid byproduct of the carbonization and vaporization process of coal, which has a pungent odor, black or blackish brown color, and a sticky liquid. The coal tar can be divided into low-temperature coal tar, medium-temperature coal tar and high-temperature coal tar according to the carbonization temperature, and the H/C atomic ratio is gradually reduced.
Compared with petroleum heavy fraction, the coal tar raw material contains oxygen, a large amount of olefin, polycyclic aromatic hydrocarbon and other unsaturated hydrocarbon and sulfur and nitrogen compounds, and has the characteristics of high acidity, high colloid content, poor product stability (light stability, storage stability, oxidation stability) and the like, so that a large amount of sulfides and nitrides can be generated by direct combustion, and serious environmental pollution is caused. The clean processing and efficient utilization of coal tar is becoming increasingly important.
The traditional processing method of coal tar aims at physically separating and extracting single-component or narrow-fraction products, and wash oil, light oil, anthracene oil, industrial naphthalene, crude phenol and inferior asphalt are extracted from the coal tar. The coal tar has complex components, low content of high added value components and high content of low added value components, is difficult to utilize, and has the technical defects of complex process flow, more equipment, high energy consumption, serious secondary pollution and poor economic benefit. The coal tar hydrogenation technology is a new exploration, and is the main direction of exploration for developing a novel coal tar cleaning utilization technology; can prolong the industrial chain, improve the utilization rate of resources, reduce pollution and extract high added value products. The ebullated bed hydrogenation has the advantages of strong raw material adaptability, no bed blockage and hot spot problems, stable product property maintenance through online catalyst feeding and discharging, prolonged operation period and the like, and is very suitable for coal tar hydrogenation processes.
Aiming at the characteristics of high oxygen content of coal tar, high sulfur and nitrogen content of metals (Fe and Ca) and high aromatic hydrocarbon content, in particular to polycyclic aromatic hydrocarbon rich in 2-4 rings and high cyclic aromatic hydrocarbon content, the prepared catalyst is required to have stronger water resistance, good hydrogenation impurity removal performance and good hydrogenation performance. For high temperature coal tar hydrogenation, the catalyst is also required to have better cracking performance. Therefore, it is an object of research to develop a coal tar hydrogenation catalyst that meets the above requirements.
CN201810576449.0 is a composite catalyst for hydrotreating-hydrocracking of ebullated bed coal tar and a preparation method thereof. In the patent, moO is used as a catalyst in percentage by mass 3 、WO 3 The composite material is prepared from NiO, alumina, a silicon oxide molecular sieve and an auxiliary agent. The patent directly mixes the molecular sieve with the raw materials, and the metal and the basic nitrogen in the coal tar are deposited on the molecular sieve, so that the catalyst is deactivated rapidly, the purposes of hydrotreating and hydrocracking are not achieved, and the preparation process of the catalyst is complex.
CN201310329947.2 a catalyst for hydrodenitrogenation of coal tar and a preparation method thereof. The catalyst consists of an active component, an auxiliary agent and a carrier, wherein the active component consists of tungsten trioxide and nickel oxide, the auxiliary agent is phosphorus, the carrier consists of active carbon, alumina and an H beta molecular sieve, the active carbon is 10-31 wt% of the carrier, the alumina is 53-82 wt% of the carrier, and the H beta molecular sieve is 8-16 wt% of the carrier. The catalyst is easy to vulcanize and has higher activity; the pore structure of the activated carbon is adjustable, which is favorable for the conversion of colloid components in coal tar and the removal of nitrogen impurities, thereby slowing down the carbon deposition of the catalyst. The catalyst in the patent cannot be directly used as a coal tar raw material, and the coal tar can be used after being hydrotreated, so that the catalyst has certain limitation in use.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a coal tar hydrogenation catalyst and a preparation method thereof. The coal tar hydrogenation catalyst provided by the invention has the advantages of high active metal utilization rate, good wear resistance, strong water resistance, high impurity removal rate, high metal capacity, good cracking performance and the like, and is suitable for coal tar hydrogenation, in particular to a fluidized bed coal tar hydrogenation process.
The invention provides a coal tar hydrogenation catalyst, which comprises a carrier and an active metal component loaded on the carrier, wherein the carrier is a silicon-aluminum material, and the active metal component is at least one of a VIB group metal and/or a VIII group metal, in particular at least one selected from Mo, W, ni, co.
In the coal tar hydrogenation catalyst, the content of the VIB group metal is 2-20wt% in terms of oxide, preferably 5-20wt%; the content of the group VIII metal is 1-10wt%, preferably 1-6wt% in terms of oxide.
In the coal tar hydrogenation catalyst, the specific properties of the catalyst are as follows: the specific surface area is 120-220 m 2 Preferably 150 to 200 m 2 The pore volume per gram is 0.4-0.8 mL/g, preferably 0.5-0.75 mL/g, the total acid value is 0.2-0.5 mol/g, preferably 0.3-0.5 mol/g, and the ratio of B acid to L acid is 0.2-0.7, preferably 0.3-0.6.
The second aspect of the invention provides a preparation method of a coal tar hydrogenation catalyst, which comprises the following steps:
s1, under the contact condition, uniformly mixing a silicon-aluminum material, a forming agent and a binder, and then forming, drying and roasting to obtain a carrier;
s2, preparing an active metal-containing solution, mixing an active metal precursor solution and a carbon precursor solution, and uniformly mixing to obtain the active metal-containing solution;
and S3, mixing the carrier obtained in the step S1 with the active metal-containing solution obtained in the step S2, and further drying and roasting to obtain the coal tar hydrogenation catalyst.
In the method for preparing the coal tar hydrogenation catalyst, the forming agent in the step S1 is one or more of cellulose and starch, preferably cellulose, and more preferably methylcellulose.
In the preparation method of the coal tar hydrogenation catalyst, the binder in the step S1 is an organic acid, and may specifically be one or more of acetic acid, citric acid, and the like, preferably citric acid.
In the preparation method of the coal tar hydrogenation catalyst, the drying temperature in the step S1 is 100-150 ℃ and the drying time is 4-10 hours.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the calcination in step S1 is performed under an inert atmosphere, and the inert atmosphere may be one or more of nitrogen and inert gas, preferably nitrogen. The roasting temperature is 500-950 ℃, preferably 550-900 ℃; the roasting time is 2-6 hours.
In the method for preparing the coal tar hydrogenation catalyst, the forming in the step S1 may be performed in a forming manner commonly used in the existing catalyst preparation, and the specific forming shape may be selected according to actual needs, for example, may be spherical, bar-shaped, clover-shaped, and the like.
Further, in the preparation method of the coal tar hydrogenation catalyst, the silicon-aluminum material in the step S1 is prepared by the following method:
(1) Adding an acidic aluminum source into a silicon source to obtain a mixed solution A,
(2) Contacting the mixed solution A with an alkaline aluminum source in the presence of water to obtain slurry B, and
(3) And carrying out hydrothermal treatment on the slurry B to obtain the silicon-aluminum material.
According to the present invention, in step (1), an acidic aluminum source is added to the silicon source, instead of adding the silicon source to the acidic aluminum source, which would otherwise result in the formation of a large amount of precipitate.
Further, in the above method for producing a coal tar hydrogenation catalyst, in the step (1), the silicon source is a water-soluble or water-dispersible basic silicon-containing compound (preferably a water-soluble or water-dispersible basic inorganic silicon-containing compound, more preferably one or more selected from water-soluble silicate, water glass and silica sol, preferably water glass).
Further, in the preparation method of the coal tar hydrogenation catalyst, the silicon source is used in the form of an aqueous solution. The silicon source (calculated as SiO 2) is present in a concentration of 5 to 30wt% (preferably 15 to 30 wt%) based on the total weight of the aqueous solution, with a modulus of typically 2.5 to 3.2.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the acidic aluminum source is a water-soluble acidic aluminum-containing compound (preferably a water-soluble acidic inorganic aluminum-containing compound, in particular a water-soluble inorganic strong acid aluminum salt, more preferably one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, preferably aluminum sulfate).
Further, in the above method for preparing a coal tar hydrogenation catalyst, the acidic aluminum source is used in the form of an aqueous solution, and the concentration of the acidic aluminum source (calculated as Al2O 3) is 30 to 100g/L (preferably 30 to 80 g/L) based on the total weight of the aqueous solution.
Further, in the preparation method of the coal tar hydrogenation catalyst, the weight ratio of the silicon source (calculated as SiO 2) to the acidic aluminum source (calculated as Al2O 3) is 1:1-9:1 (preferably 1:1-7:1).
Furthermore, in the preparation method of the coal tar hydrogenation catalyst, in order to achieve more excellent technical effects of the invention, in particular to obtain a silicon-aluminum material with larger pore volume and lower impurity content, in the step (1), an acid is further added (preferably, the acidic aluminum source is added to the silicon source, and then the acid is added to obtain the mixed solution A).
Further, in the above method for preparing a coal tar hydrogenation catalyst, the acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid and hydrochloric acid, preferably sulfuric acid).
Further, in the above method for preparing a coal tar hydrogenation catalyst, the acid is used in the form of an aqueous solution. The concentration of the acid is 2-6wt% (preferably 2-5 wt%wt) based on the total weight of the aqueous solution.
Further, in the preparation method of the coal tar hydrogenation catalyst, the acid is added in an amount such that the pH value of the mixed solution A is 2-4 (preferably 3-4).
In the method for preparing the coal tar hydrogenation catalyst, in the step (1), in general, the aluminum content of the mixed solution A is 5-20g Al2O3/L calculated by Al2O3, and the silicon content is 5-40g SiO2/L calculated by SiO 2.
Further, in the above method for preparing a coal tar hydrogenation catalyst, in the step (2), the alkaline aluminum source is a water-soluble alkaline aluminum-containing compound (preferably a water-soluble alkaline inorganic aluminum-containing compound, especially an alkali metal meta-aluminate, more preferably one or more selected from sodium meta-aluminate and potassium meta-aluminate, and preferably sodium meta-aluminate).
Further, in the preparation method of the coal tar hydrogenation catalyst, the alkaline aluminum source is used in the form of an aqueous solution. The alkaline aluminium source (calculated as Al2O 3) has a concentration of 130-350g/L (preferably 150-250 g/L) and a caustic ratio of generally 1.15-1.35, preferably 1.15-1.30, based on the total weight of the aqueous solution.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the amount of the mixed solution a is 40 to 70vol% (preferably 40 to 65 vol%) based on the total volume of the mixed solution a, the alkaline aluminum source and water.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the amount of the alkaline aluminum source is 20 to 40vol% (preferably 25 to 40 vol%) based on the total volume of the mixed solution a, the alkaline aluminum source and water.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the amount of water used is 10 to 20vol% (preferably 13 to 20 vol%) based on the total volume of the mixed solution a, the alkaline aluminum source and water.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the mixed solution a and the alkaline aluminum source are added to water sequentially or simultaneously (preferably, the mixed solution a and the alkaline aluminum source are added to water in a parallel flow mode).
Further, in the preparation method of the coal tar hydrogenation catalyst, the adding flow rate of the mixed solution A is 15-50mL/min (preferably 20-40 mL/min).
Further, in the above method for preparing a coal tar hydrogenation catalyst, the flow rate of the alkaline aluminum source is controlled so that the pH of the slurry B is maintained at 7.5 to 10.5 (preferably 8.0 to 10.5, more preferably 8.5 to 10.5).
Furthermore, in the preparation method of the coal tar hydrogenation catalyst, in order to achieve more excellent technical effects of the invention, particularly to obtain a silicon-aluminum material with larger pore volume, in the step (2), water-soluble carbonate is further added (preferably, the mixed solution A and the alkaline aluminum source are added into water, and then the water-soluble carbonate is added to obtain the slurry B).
Further, in the above method for preparing the coal tar hydrogenation catalyst, the water-soluble carbonate is selected from one or more carbonates of alkali metal and ammonium (preferably one or more carbonates selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate, preferably sodium carbonate).
Further, in the preparation method of the coal tar hydrogenation catalyst, the water-soluble carbonate is used in a solid form.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the water-soluble carbonate is added in an amount such that the pH value of the slurry B is 10.5-12 (preferably 11-12).
In the method for preparing the coal tar hydrogenation catalyst, in the step (3), the silicon-aluminum material is separated from the reaction system of the hydrothermal treatment, washed to be neutral, and then dried. The washing may be carried out by a washing method conventional in the art, preferably deionized water, and more preferably at 50 to 90 ℃. In addition, the separation can adopt any means in the field for realizing the separation of liquid-solid two-phase materials, such as filtration, centrifugal separation and the like, and particularly, the separation can be carried out in a filtration separation mode in the invention, so as to obtain a solid-phase material and a liquid-phase material after separation, and the solid-phase material is washed and dried to obtain the silicon-aluminum material.
Further, in the preparation method of the coal tar hydrogenation catalyst, the drying conditions include: the drying temperature is 100-150deg.C, and the drying time is 6-10 hr.
Further, in the preparation method of the coal tar hydrogenation catalyst, in the step (1), the temperature is 25-50 ℃ (preferably 25-40 ℃) and the pressure is normal pressure.
Further, in the preparation method of the coal tar hydrogenation catalyst, in the step (2), the temperature is 50-90 ℃ (preferably 50-80 ℃), and the pressure is normal pressure.
Further, in the above-mentioned method for preparing a coal tar hydrogenation catalyst, in the step (3), the temperature is 180 to 300 ℃ (preferably 180 to 280 ℃, more preferably 180 to 250 ℃), and the pressure is 0.1 to 0.5MPa (preferably 0.1 to 0.3 MPa).
Furthermore, in the preparation method of the coal tar hydrogenation catalyst, in order to achieve the technical effect of the invention more excellent, in the step (3), the time of the hydrothermal treatment is 0.5-15h (preferably 0.5-12 h). Furthermore, in the preparation method of the coal tar hydrogenation catalyst, one or more auxiliary agents such as P2O5, B2O3 or TiO2 can be added according to actual needs. For this purpose, these precursors may be added in the form of water-soluble inorganic salts during the reaction of step (1). Examples of the inorganic salt include borates, sulfates, nitrates, and the like. In addition, the addition amount of the auxiliary agents can be arbitrarily adjusted according to the requirements of the subsequent catalysts and the like. In general, these auxiliaries are generally present in amounts of from 1 to 8% by weight, preferably from 2 to 6% by weight, based on the oxides, relative to 100% by weight of the total weight of the silicon-aluminum material.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the active metal in step S2 is at least one selected from the group consisting of group VIB metals and/or group VIII metals, especially at least one selected from the group consisting of Mo, W, ni, co. Further, the active metal precursor can be Mo-Ni (Co) -P heteropolyacid solution or Mo (W) -Ni (Co) -NH 3· H 2 O alkaline active metal solution.
Further, in the above method for preparing a coal tar hydrogenation catalyst, the carbon precursor solution in step S2 may be one or more of an organic acid and an alcohol. Specifically, the carbon precursor can be one or more of citric acid, tartaric acid, ethanol and ethylene glycol, and the addition amount of the carbon precursor is 5-20wt%, preferably 10-20wt% of the active metal content.
In the method for preparing the coal tar hydrogenation catalyst, the carrier obtained in the step S1 in the step S3 may be mixed with the active metal-containing solution obtained in the step S2 by an impregnation method.
In the preparation method of the coal tar hydrogenation catalyst, the drying temperature in the step S3 is 100-150 ℃ and the drying time is 4-10 hours.
Further, in the preparation method of the coal tar hydrogenation catalyst, the roasting in the step S3 is performed under the condition of a vapor-containing gas, wherein the vapor-containing gas is a mixed gas of vapor and carrier gas, and the carrier is one or more of nitrogen, helium, neon, argon, krypton and xenon, preferably nitrogen. The volume ratio of the carrier to the water vapor is 5: 1-1:2.
In the preparation method of the coal tar hydrogenation catalyst, the roasting temperature in the step S3 is 400-650 ℃, preferably 400-550 ℃; roasting for 3-8 hours.
The third aspect of the invention provides a coal tar hydrogenation process, which comprises the step of carrying out contact reaction on coal tar and hydrogen-containing gas under hydrogenation reaction conditions in the presence of the coal tar hydrogenation catalyst or the coal tar hydrogenation catalyst obtained according to the preparation method.
In the coal tar hydrogenation process, the coal tar material may be at least one selected from low-temperature coal tar, medium-temperature coal tar and high-temperature coal tar.
In the coal tar hydrogenation process, the hydrogen-containing gas is hydrogen or a mixed gas of hydrogen and other gases, and the volume content of hydrogen in the mixed gas is generally not less than 80%, preferably not less than 85%, and more preferably not less than 95%.
In the coal tar hydrogenation process, the hydrogenation reaction conditions are as follows: the reaction pressure is 5-20 MPaG, the reaction temperature is 300-420 ℃, and the liquid hourly space velocity is 0.1-1.5 h -1 The volume ratio of the hydrogen oil is 100-1000.
Compared with the prior art, the coal tar hydrogenation catalyst and the preparation method thereof have the following advantages:
1. According to the preparation method of the coal tar hydrogenation catalyst, the carbon precursor is introduced into the active metal solution, and then the carbon precursor is baked under the inert atmosphere, so that a carbon layer can be formed on the surface of the carrier, the water resistance of the carrier is increased, meanwhile, the carbon layer of the carrier can weaken the interaction between the active metal and the carrier in the impregnation process, and simultaneously, carbon-containing substances in the impregnation liquid are baked under the atmosphere of nitrogen and water vapor to prevent aggregation of the metal, so that the utilization rate of the active metal is improved, the active metal is easier to vulcanize, and the hydrogenation performance of the catalyst is improved. The catalyst is treated under the condition of water vapor, so that the structure of the catalyst is more easily stabilized, and the catalyst is very suitable for coal tar hydrogenation technology with high oxygen content.
2. In the preparation method of the coal tar hydrogenation catalyst provided by the invention, a silicon source adopts a method of firstly acidic aluminum source and then inorganic acid acidification in the preparation process of the silicon-aluminum material, so that cations (sodium ions and the like) in silicic acid polymers enveloped in rings or cages in the silicon source are dissociated, acidified silica gel groups are adsorbed on aluminum hydroxide colloid, so that the sodium ions are effectively separated from the silica gel groups, and an acidic aluminum solution is added to play a role of isolating the dissociated cations, so that the subsequent removal of the cations (sodium ions) is easier, the subsequent difficulty of washing and removing sodium is greatly reduced, and the washing water consumption is reduced. More importantly, cations (sodium ions) can be effectively removed, the acidic position occupied by Na can be recovered, so that the silicon-aluminum material has higher acidity, and the obtained silicon-aluminum material has the characteristics of large pore volume, mesoporous-macroporous multi-stage pore canal, high B acid content, high crystallinity, low impurity content (especially low sodium content), good hydrothermal stability and the like.
3. In the preparation method of the coal tar hydrogenation catalyst provided by the invention, the acidified silica gel groups are adsorbed on the aluminum hydroxide colloid in the preparation process of the silicon-aluminum material, so that crystal nuclei are provided for subsequent reactions, the grain size of the prepared silicon-aluminum material is promoted to be increased, and the silicon-aluminum material with large pore volume and large pore diameter is formed.
4. In the preparation method of the coal tar hydrogenation catalyst provided by the invention, the pH value of the slurry B is regulated in the preparation process of the silicon-aluminum material, the slurry system form is changed from the initial state of fluidity to the state of gel-like thixotropy in the high-temperature treatment process, the slurry system is changed into the state of fluidity after a period of treatment, and the silicon-aluminum material and water form a changeable silicon-aluminum-oxygen network structure in the process of changing into the state of gel-like thixotropy, so that the preparation of the silicon-aluminum material with large pore volume is facilitated.
Detailed Description
The following detailed description of the invention is made by way of specific examples, but it should be noted that the scope of the invention is not limited by these embodiments but is defined by the claims.
In the context of this specification, the pore volume, specific surface area and pore size distribution of the silica-alumina material and catalyst are measured using a low temperature nitrogen adsorption method. Total acid, B acid and L acid were measured by pyridine IR adsorption. Sodium oxide and silica were measured using fluorescence analysis. The active metal content is measured spectrophotometrically. The wear index was measured using an air jet method.
All percentages, parts, ratios, etc. referred to in this specification are by weight and pressure is gauge unless explicitly indicated.
Any two or more embodiments of the invention may be combined in any desired manner within the context of this specification, and the resulting solution is part of the original disclosure of this specification, while still falling within the scope of the invention.
Example 1
(1) Preparation of silicon-aluminum material
The concentration of the mixture is 80gAl 2 O 3 Aluminum sulfate solution/L and a concentration of 50gSiO 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use, and preparing a dilute sulfuric acid solution with the concentration of 0.5mol/L for later use. Preparation of caustic ratio 1.15, concentration 180 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
1.0L of 50g SiO concentration is measured 2 adding/L silica sol solution into a container, slowly adding 0.8L of 80g Al under stirring 2 O 3 Aluminum sulfate solution/L, which has been colloidal in aluminum hydroxide, but the solution is still in liquid form. Then adding 1mol/L dilute sulfuric acid solution, adjusting the pH to 3.5, and completing the acidification treatment to obtain a mixed solution A.
1000mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, after the deionized water is heated to 60 ℃, the mixed solution A is added into the reactor at 20mL/min, meanwhile, the prepared sodium metaaluminate solution is added in parallel flow, the pH value of the reaction is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction was completed, the amount of sodium metaaluminate was 640mL, and 41g of ammonium carbonate was added to the reactor with stirring to adjust the pH to 10.5. The slurry is put into a reactor, and the treatment temperature is 210 ℃ and the treatment pressure is 0.2MPa under the condition of stirring, and the treatment is carried out for 2 hours. Washing the treated slurry with hot water at 90 ℃ until the slurry is neutral, drying at 120 ℃ for 6 hours to obtain a dried sample PO-1, and roasting at 600 ℃ for 5 hours to obtain a silicon aluminum material P-1, wherein the properties are shown in Table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of prepared PO-1 silicon aluminum dried sample, adding 8.2g of methyl cellulose, 11.96g of citric acid and 470g of purified water, uniformly mixing and then forming a ball shape. The sample was dried at 130℃for 5h and then calcined at 800℃for 4 hours under a nitrogen atmosphere to give a carrier Z1 having a particle size of 0.7 to 1.2 mm.
98.32g of phosphoric acid is weighed, 1800mL of distilled water is added, 213.64g of molybdenum oxide and 97.37g of basic nickel carbonate are sequentially added, and the mixture is heated and stirred until the mixture is completely dissolved. Then, 30.93g of citric acid was added and dissolved with stirring, and the solution was fixed to 2000mL with distilled water to obtain solution L1.
The support Z1 was saturated with the solution L1 solution and dried at 110℃for 2h. The volume ratio of nitrogen to water vapor is 3: roasting for 3 hours at the temperature of 1 and 450 ℃ to obtain the catalyst C1, wherein the specific properties are shown in Table 2.
Example 2
Other conditions were the same as in example 1, except that: changing silica sol into water glass solution, changing the adding amount of bottom water of a reactor into 800ml, controlling the pH of the reaction into 8.5 to obtain a silica-alumina material dried sample PO-2, and roasting at 600 ℃ for 5 hours to obtain the silica-alumina material P-2, wherein the properties are shown in Table 1.
Taking 500g of prepared PO-2 silicon aluminum dried sample, adding 5.14g of corn starch, 9.85g of acetic acid (85 wt%) and 480g of water, uniformly mixing, forming into a ball, and roasting the ball-formed sample at 700 ℃ for 5h to obtain a carrier Z2 with the granularity of 0.7-1.2 mm.
The support Z2 was saturated with the solution L1 and dried at 110℃for 2h. The volume ratio of nitrogen to water vapor is 2: roasting for 4 hours at the temperature of 1 and 500 ℃ to obtain a catalyst C2, wherein the specific properties are shown in Table 2.
Example 3
Other conditions were the same as in example 1, except that: the concentration of the silica sol solution is changed to 70SiO 2 and/L, then adding 1mol/L dilute sulfuric acid solution, adjusting the pH value to be 4.0, adding the mixed solution A at 25mL/min, treating at 250 ℃ under 0.4MPa for 4 hours to obtain a silicon-aluminum material dried sample PO-3, and roasting at 600 ℃ for 5 hours to obtain the silicon-aluminum material P-3, wherein the properties are shown in Table 1.
Taking 500g of prepared PO-3 silicon aluminum dried sample, adding 6.15g of methyl cellulose, 12.42g of tartaric acid and 460g of water, uniformly mixing, forming a ball, and roasting the ball-formed sample at 650 ℃ for 4 hours to obtain a carrier Z3 with the granularity of 0.7-1.2 mm.
The support Z3 was saturated with the solution L1 and dried at 110℃for 2h. The volume ratio of nitrogen to water vapor is 1: roasting for 3 hours at 1 and 480 ℃ to obtain a catalyst C3, wherein the specific properties are shown in Table 2.
Example 4
(1) Preparation of silicon-aluminum material
The concentration of the preparation is 30gAl 2 O 3 Aluminum sulfate solution/L and 60g SiO concentration 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use, and preparing a dilute nitric acid solution with the concentration of 1.5mol/L for later use. Preparation of caustic ratio 1.20, concentration 150 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
1.5L of 60g SiO concentration was measured 2 adding/L silica sol solution into a container, slowly adding 1.0L of 30g Al under stirring 2 O 3 Aluminum sulfate solution/L, which has been colloidal in aluminum hydroxide, but the solution is still in liquid form. Then, 1.5mol/L of dilute nitric acid is used, the pH is adjusted to 3.0, and the acidification treatment is completed, so that the mixed solution A is obtained.
800mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, after the deionized water is heated to 70 ℃, the mixed solution A is added into the reactor at 15mL/min, meanwhile, the prepared sodium metaaluminate solution is added in parallel flow, the pH value of the reaction is controlled to 8.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction was completed, the amount of sodium metaaluminate was 690mL, and 72g of ammonium carbonate was added to the reactor with stirring to adjust the pH to 10.0. The slurry is put into a reactor, and the treatment temperature is 250 ℃ and the treatment pressure is 0.3MPa under the condition of stirring, and the treatment is carried out for 3 hours. Washing the treated slurry with hot water at 90 ℃ until the slurry is neutral, drying at 120 ℃ for 6 hours to obtain a dried sample PO-4, and roasting at 600 ℃ for 5 hours to obtain a silicon aluminum material P-4, wherein the properties are shown in Table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of prepared PO-4 silicon aluminum dried sample, adding 7.00g of wheat starch, 12.35g of acetic acid (85%) and 490g of purified water, uniformly mixing and forming a ball. The sample was dried at 130℃for 5h and then calcined at 750℃for 3 hours under a nitrogen atmosphere to give a carrier Z4 having a particle size of 0.7 to 1.2 mm.
81.53g of phosphoric acid is weighed, 1000mL of distilled water is added, 221.43g of molybdenum oxide and 81.19g of basic nickel carbonate are sequentially added, and the mixture is heated and stirred until the mixture is completely dissolved. Then 39.45g of ethylene glycol was added and dissolved with stirring, and the solution was fixed to 1000mL with distilled water to obtain solution L2.
The support Z4 was saturated with the solution L2 and dried at 110℃for 2h. The volume ratio of nitrogen to water vapor is 1: roasting at 1 and 600 ℃ for 3 hours to obtain a catalyst C4, wherein the specific properties are shown in Table 2.
Example 5
Other conditions were the same as in example 4, except that: changing the silica sol solution into water glass with the concentration of 50SiO 2 and/L, adding the mixed solution A at 25mL/min, wherein the treatment temperature is 210 ℃, the treatment pressure is 0.4MPa, the treatment is carried out for 4 hours, a silicon-aluminum material dried sample PO-5 is obtained, and the roasting is carried out for 5 hours at 600 ℃ to obtain the silicon-aluminum material P-5, and the properties are shown in the table 1.
Taking 500g of prepared PO-5 silicon aluminum dried sample, adding 8.23g of methyl cellulose, 10.15g of citric acid and 500g of water, uniformly mixing, forming a ball, and roasting the ball-formed sample at 700 ℃ for 4 hours to obtain a carrier Z5 with the granularity of 0.7-1.2 mm.
The support Z5 was saturated with the solution L2 and dried at 110℃for 2h. The volume ratio of nitrogen to water vapor is 1:2, roasting at 450 ℃ for 4 hours to obtain a catalyst C5, wherein the specific properties are shown in Table 2.
Comparative example 1
(1) Preparation of silicon-aluminum material
The concentration of the mixture is 80gAl 2 O 3 Aluminum sulfate solution/L and a concentration of 50gSiO 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use. Preparation of caustic ratio 1.15, concentration 180 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
1000mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, aluminum sulfate is added into the reactor at 20mL/min and 30mL/min of silica sol after the deionized water is heated to 60 ℃, meanwhile, the prepared sodium metaaluminate solution is added in parallel, the pH value of the reaction is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction was completed, the amount of sodium metaaluminate was 640mL, and 41g of ammonium carbonate was added to the reactor with stirring to adjust the pH to 10.5. The slurry is put into a reactor, and the treatment temperature is 210 ℃ and the treatment pressure is 0.2MPa under the condition of stirring, and the treatment is carried out for 2 hours. Washing the treated slurry with hot water at 90 ℃ until the slurry is neutral, drying at 120 ℃ for 6 hours to obtain a dried sample PFO-1, and roasting at 600 ℃ for 5 hours to obtain a silica-alumina material PF-1, wherein the properties of the silica-alumina material PF-1 are shown in Table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of prepared PO-1 silicon aluminum dried sample, adding 8.2g of methyl cellulose, 11.96g of citric acid and 470g of purified water, uniformly mixing and then forming a ball shape. The sample was dried at 130℃for 5 h and then calcined at 800℃for 4 hours under a nitrogen atmosphere to give carrier ZF1 having a particle size of 0.7-1.2 mm.
98.32g of phosphoric acid is weighed, 1800mL of distilled water is added, 213.64g of molybdenum oxide and 97.37g of basic nickel carbonate are sequentially added, and the mixture is heated and stirred until the mixture is completely dissolved. Then, 30.93g of citric acid was added and dissolved with stirring, and the solution was fixed to 2000mL with distilled water to obtain solution L1.
The carrier ZF1 was saturated impregnated with the solution L1 solution and dried at 110℃for 2h. Roasting for 3 hours at 450 ℃ under nitrogen atmosphere to obtain the catalyst CF1, wherein the specific properties are shown in Table 2.
Comparative example 2
(1) Preparation of silicon-aluminum material
The concentration of the mixture is 80gAl 2 O 3 Aluminum sulfate solution/L and a concentration of 50gSiO 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use, and preparing a dilute sulfuric acid solution with the concentration of 0.5mol/L for later use. Preparation of caustic ratio 1.15, concentration 180 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
0.8L of 80gAl concentration is measured 2 O 3 adding/L aluminum sulfate solution into a container, slowly adding 1.0L of 50g SiO under stirring 2 Silica sol solution of/L, the process generates a large amount of aluminum hydroxide gel, and the fluidity is poor. Then addAnd (3) regulating the pH to 3.5 by 1mol/L dilute sulfuric acid solution, and completing the acidification treatment to obtain a mixed solution A.
1000mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, after the deionized water is heated to 60 ℃, the mixed solution A is added into the reactor at 20mL/min, meanwhile, the prepared sodium metaaluminate solution is added in parallel flow, the pH value of the reaction is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction was completed, the amount of sodium metaaluminate was 640mL, and 41g of ammonium carbonate was added to the reactor with stirring to adjust the pH to 10.5. The slurry is put into a reactor, and the treatment temperature is 210 ℃ and the treatment pressure is 0.2MPa under the condition of stirring, and the treatment is carried out for 2 hours. The treated slurry was washed with hot water at 90℃until liquid neutral, dried at 120℃for 6 hours to give dried sample PFO-2, and calcined at 600℃for 5 hours to give silica alumina material PF-2, the properties of which are shown in Table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of prepared PFO-2 silicon aluminum dry sample, adding 8.2g of methyl cellulose, 11.96g of citric acid and 470g of purified water, uniformly mixing and then forming a ball shape. The sample was dried at 130℃for 5h and then calcined at 800℃for 4 hours under a nitrogen atmosphere to give carrier ZF2 having a particle size of 0.7-1.2 mm.
98.32g of phosphoric acid is weighed, 1800mL of distilled water is added, 213.64g of molybdenum oxide and 97.37g of basic nickel carbonate are sequentially added, and the mixture is heated and stirred until the mixture is completely dissolved. Then, 30.93g of citric acid was added and dissolved with stirring, and the solution was fixed to 2000mL with distilled water to obtain solution L1.
The carrier ZF2 was saturated impregnated with the solution L1 solution and dried at 110℃for 2h. Roasting for 3 hours at 450 ℃ under nitrogen atmosphere to obtain the catalyst CF2, wherein the specific properties are shown in Table 2.
Comparative example 3
(1) Preparation of silicon-aluminum material
The concentration of the mixture is 80gAl 2 O 3 Aluminum sulfate solution/L and a concentration of 50gSiO 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use, and preparing a dilute sulfuric acid solution with the concentration of 0.5mol/L for later use. Preparation of caustic ratio 1.15, concentration 180 gAl 2 O 3 Aluminum bias of/LAnd (5) sodium acid solution for standby.
1.0L of 50g SiO concentration is measured 2 adding/L silica sol solution into a container, slowly adding 0.8L of 80g Al under stirring 2 O 3 Aluminum sulfate solution/L, which has been colloidal in aluminum hydroxide, but the solution is still in liquid form. Then adding 1mol/L dilute sulfuric acid solution, adjusting the pH to 3.5, and completing the acidification treatment to obtain a mixed solution A.
1000mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, after the deionized water is heated to 60 ℃, the mixed solution A is added into the reactor at 20mL/min, meanwhile, the prepared sodium metaaluminate solution is added in parallel flow, the pH value of the reaction is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction is finished, the dosage of sodium metaaluminate is 640mL.
Washing the reacted slurry with hot water at 90 ℃ until the slurry is neutral, drying the slurry at 120 ℃ for 6 hours to obtain a dried sample PFO-3, and roasting the dried sample PFO-3 at 600 ℃ for 5 hours to obtain a silicon-aluminum material PF-3, wherein the properties of the silicon-aluminum material PF-3 are shown in Table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of prepared PFO-3 silicon aluminum dry sample, adding 8.2g of methyl cellulose, 11.96g of citric acid and 470g of purified water, uniformly mixing and then forming a ball shape. The sample was dried at 130℃for 5h and then calcined at 800℃for 4 hours under a nitrogen atmosphere to give carrier ZF3 having a particle size of 0.7-1.2 mm.
98.32g of phosphoric acid is weighed, 1800mL of distilled water is added, 213.64g of molybdenum oxide and 97.37g of basic nickel carbonate are sequentially added, and the mixture is heated and stirred until the mixture is completely dissolved. Then, 30.93g of citric acid was added and dissolved with stirring, and the solution was fixed to 2000mL with distilled water to obtain solution L1.
The carrier ZF3 was saturated impregnated with the solution L1 solution and dried at 110℃for 2h. Roasting for 3 hours at 450 ℃ under nitrogen atmosphere to obtain the catalyst CF3, wherein the specific properties are shown in Table 2.
TABLE 1 Properties of silicon aluminum materials
TABLE 2 Properties of the catalysts
The activity of the catalyst was evaluated on a continuous tank reactor (CSTR) device, and medium-low temperature coal tar was used for the evaluation, and the properties and evaluation conditions are shown in Table 3. The production oil was sampled and analyzed for 1000 hours of operation, and the results of other evaluations after comparing the activity with that of comparative example 3 are shown in Table 4, with the activity of comparative example 3 being 100.
Table 3 medium and low temperature coal tar properties and evaluation conditions
Table 4 results of catalyst evaluation
From the data in each table, it can be seen that: the silicon-aluminum material prepared by the method has large pore volume, small proportion of <10nm pores, low sodium oxide content and high B acid content. Compared with the catalyst prepared by the comparative example, the coal tar hydrogenation catalyst prepared by the silicon-aluminum material increases the impurity removal rate, particularly the removal of metal iron and calcium, and the medium-low temperature coal tar is effectively converted, thereby providing high-quality raw materials for subsequent product processing.
Claims (42)
1. The catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the carrier is a silicon-aluminum material, and the active metal component is at least one of VIB metal element Mo, VIB metal element W, VIII metal element Ni and VIII metal element Co; the catalyst properties were as follows: the specific surface area is 120-220 m 2 Per g, pore volume of 0.4-0.8 mL/g, total acid value of 0.2-0.5 mol/g, ratio of B acid to L acid of 0.20.7; the silicon-aluminum material is prepared by the following method:
(1) Adding an acidic aluminum source into a silicon source to obtain a mixed solution A,
(2) Contacting the mixed solution A with an alkaline aluminum source in the presence of water to obtain slurry B, and
(3) And carrying out hydrothermal treatment on the slurry B to obtain the silicon-aluminum material.
2. The coal tar hydrogenation catalyst according to claim 1, wherein the content of the group VIB metal is 2 to 20wt% in terms of oxide, and the content of the group VIII metal is 1 to 10wt% in terms of oxide.
3. The coal tar hydrogenation catalyst according to claim 1 or 2, wherein the group VIB metal is contained in an amount of 5 to 20wt% in terms of oxide; the content of the VIII group metal is 1-6wt% calculated by oxide.
4. The coal tar hydrogenation catalyst according to claim 1, wherein the catalyst properties are as follows: specific surface area of 150-200 m 2 The pore volume per gram is 0.5-0.75 mL/g, the total acid value is 0.3-0.5 mol/g, and the ratio of B acid to L acid is 0.3-0.6.
5. The method for preparing the coal tar hydrogenation catalyst of claim 1, which comprises the following steps:
s1, under the contact condition, uniformly mixing a silicon-aluminum material, a forming agent and a binder, and then forming, drying and roasting to obtain a carrier;
s2, preparing an active metal-containing solution, mixing an active metal precursor solution and a carbon precursor solution, and uniformly mixing to obtain the active metal-containing solution;
and S3, mixing the carrier obtained in the step S1 with the active metal-containing solution obtained in the step S2, and further drying and roasting to obtain the coal tar hydrogenation catalyst.
6. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the forming agent in the step S1 is one or more of cellulose and starch.
7. The method for preparing a coal tar hydrogenation catalyst according to claim 5 or 6, wherein the shaping agent in step S1 is cellulose.
8. The method for preparing a coal tar hydrogenation catalyst according to claim 7, wherein the shaping agent in step S1 is methylcellulose.
9. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the binder in the step S1 is an organic acid, and the organic acid is one or more selected from acetic acid and citric acid.
10. The method for preparing a coal tar hydrogenation catalyst according to claim 5 or 9, wherein the binder in step S1 is citric acid.
11. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the drying temperature in the step S1 is 100-150 ℃.
12. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the calcination in step S1 is performed under an inert atmosphere, which is one or more of nitrogen and inert gas; the roasting temperature is 500-950 ℃.
13. The method for preparing a coal tar hydrogenation catalyst according to claim 12, wherein the inert atmosphere is nitrogen; the roasting temperature is 550-900 ℃.
14. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the silicon-aluminum material in step S1 is prepared by the following method:
(1) Adding an acidic aluminum source into a silicon source to obtain a mixed solution A,
(2) Contacting the mixed solution A with an alkaline aluminum source in the presence of water to obtain slurry B, and
(3) And carrying out hydrothermal treatment on the slurry B to obtain the silicon-aluminum material.
15. The method for producing a coal tar hydrogenation catalyst according to claim 14, wherein the silicon source in step (1) is a water-soluble or water-dispersible basic silicon-containing compound, and/or the silicon source is used in the form of an aqueous solution, and the silicon source is used as SiO based on the total weight of the aqueous solution 2 At a concentration of 5 to 30 wt.% and/or a modulus of 2.5 to 3.2 and/or the acidic aluminum source is a water-soluble acidic aluminum-containing compound and/or the acidic aluminum source is used in the form of an aqueous solution and is present as Al based on the total weight of the aqueous solution 2 O 3 At a concentration of 30-100g/L, and/or the silicon source is in the form of SiO 2 Counting the acid aluminum source and the acid aluminum source by Al 2 O 3 The weight ratio of the two components is 1:1-9:1.
16. The method for producing a coal tar hydrogenation catalyst according to claim 14 or 15, wherein the silicon source in step (1) is a water-soluble or water-dispersible basic inorganic silicon-containing compound, and/or the silicon source is used in the form of an aqueous solution, and the silicon source is used as SiO based on the total weight of the aqueous solution 2 At a concentration of 15 to 30wt%, and/or the acidic aluminum source is a water-soluble acidic inorganic aluminum-containing compound, and/or the acidic aluminum source is used in the form of an aqueous solution, and the acidic aluminum source is used as Al based on the total weight of the aqueous solution 2 O 3 At a concentration of 30-80g/L, and/or the silicon source is SiO 2 Counting the acid aluminum source and the acid aluminum source by Al 2 O 3 The weight ratio of the two components is 1:1-7:1.
17. The method for preparing a coal tar hydrogenation catalyst according to claim 14 or 15, wherein the silicon source in the step (1) is selected from one or more of water-soluble silicate and silica sol, and/or the acidic aluminum source is one or more of aluminum sulfate, aluminum nitrate and aluminum chloride.
18. The method for preparing a coal tar hydrogenation catalyst according to claim 17, wherein the silicon source in the step (1) is water glass and/or the acidic aluminum source is aluminum sulfate.
19. The method for preparing a coal tar hydrogenation catalyst according to claim 14, wherein an acid is added in the step (1), and/or the acid is a water-soluble acid, and/or the acid is used in the form of an aqueous solution, and the concentration of the acid is 2 to 6wt% based on the total weight of the aqueous solution, and/or the acid is added in such an amount that the pH of the mixed liquor a is 2 to 4.
20. The method for producing a coal tar hydrogenation catalyst according to claim 14 or 19, wherein in step (1), the acidic aluminum source is added to the silicon source, and then an acid is added to obtain the mixed liquor a, and/or the acid is a water-soluble inorganic acid, and/or the acid is used in the form of an aqueous solution and the concentration of the acid is 2 to 5% by weight based on the total weight of the aqueous solution, and/or the acid is added in such an amount that the pH value of the mixed liquor a is 3 to 4.
21. The method for preparing a coal tar hydrogenation catalyst according to claim 20, wherein the acid is one or more of sulfuric acid, nitric acid and hydrochloric acid.
22. The method for preparing a coal tar hydrogenation catalyst according to claim 21, wherein the acid is sulfuric acid.
23. The method for producing a coal tar hydrogenation catalyst according to claim 14, wherein the basic aluminum source in step (2) is a water-soluble basic aluminum-containing compound, and/or the basic aluminum source is used in the form of an aqueous solution, and the basic aluminum source is used as Al based on the total weight of the aqueous solution 2 O 3 The concentration is 130-350g/L, the caustic ratio is 1.15-1.35, and/or the amount of the mixed liquor A is 40-70vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the amount of the alkaline aluminum source is 20-40vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the amount of the water is 10-20vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the mixed liquor A and the alkaline aluminum source are added to the water sequentially or simultaneously, and/or the adding flow rate of the mixed liquor A is 15-50mL/min, and/or the adding flow rate of the alkaline aluminum source is controlled so that the pH value of the slurry B is maintained at 7.5-10.5.
24. The method for producing a coal tar hydrogenation catalyst according to claim 14 or 23, wherein the basic aluminum source in step (2) is a water-soluble basic inorganic aluminum-containing compound, and/or the basic aluminum source is used in the form of an aqueous solution, and the basic aluminum source is used as Al based on the total weight of the aqueous solution 2 O 3 The concentration is 150-250g/L, the caustic ratio is 1.15-1.3, and/or the amount of the mixed liquor A is 40-65vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the amount of the alkaline aluminum source is 25-40vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the amount of the water is 13-20vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the mixed liquor A and the alkaline aluminum source are added to the water in a parallel flow mode, and/or the adding flow rate of the mixed liquor A is 20-40mL/min, and/or the adding flow rate of the alkaline aluminum source is controlled, so that the pH value of the slurry B is maintained at 8.0-10.5.
25. The method for producing a coal tar hydrogenation catalyst according to claim 24, wherein in the step (2), the alkaline aluminum source is an alkali metal meta-aluminate selected from one or more of sodium meta-aluminate and potassium meta-aluminate, and/or the flow rate of addition of the alkaline aluminum source is controlled so that the pH of the slurry B is maintained at 8.5 to 10.5.
26. The method for producing a coal tar hydrogenation catalyst according to claim 14, wherein a water-soluble carbonate is further added in the step (2), and/or the water-soluble carbonate is selected from one or more of alkali metal and ammonium carbonates, and/or the water-soluble carbonate is used in a solid form, and/or the water-soluble carbonate is added in such an amount that the pH of the slurry B is 10.5 to 12.
27. The method for producing a coal tar hydrogenation catalyst according to claim 14 or 26, wherein in the step (2), the mixed solution a and the alkaline aluminum source are added to water, and then a water-soluble carbonate is added to obtain the slurry B, and/or the water-soluble carbonate is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, and/or the water-soluble carbonate is used in a solid form, and/or the water-soluble carbonate is added in such an amount that the pH of the slurry B is 11 to 12.
28. The method for preparing a coal tar hydrogenation catalyst according to claim 14, wherein the silica-alumina material is separated from the reaction system of the hydrothermal treatment in step (3), washed to be neutral, and then dried, and/or the drying conditions include: the drying temperature is 100-150deg.C, and the drying time is 6-10 hr.
29. The method for preparing a coal tar hydrogenation catalyst according to claim 14, wherein the temperature is 25 to 50 ℃ and the pressure is normal pressure in the step (1), and/or the temperature is 50 to 90 ℃ and the pressure is normal pressure in the step (2), and/or the temperature is 180 to 300 ℃ and the pressure is 0.1 to 0.5MPa in the step (3), and/or the time of the hydrothermal treatment is 0.5 to 15 hours in the step (3).
30. The method for producing a coal tar hydrogenation catalyst according to claim 14 or 29, wherein the temperature is 25 to 40 ℃ and the pressure is normal pressure in step (1), and/or the temperature is 50 to 80 ℃ and the pressure is normal pressure in step (2), and/or the temperature is 180 to 280 ℃ and the pressure is 0.1 to 0.3MPa in step (3), and/or the time of the hydrothermal treatment is 0.5 to 12 hours in step (3).
31. The method for preparing a coal tar hydrogenation catalyst according to claim 14 or 29, wherein in step (3), the temperature is 180 to 250 ℃.
32. The method for preparing a coal tar hydrogenation catalyst according to claim 14, wherein an auxiliary agent is further added, the auxiliary agent being selected from one or more of phosphorus, boron and titanium, and/or the auxiliary agent being contained in an amount of 1 to 8wt% in terms of oxide, based on 100wt% of the total weight of the silicon-aluminum material.
33. The method for preparing a coal tar hydrogenation catalyst according to claim 32, wherein the auxiliary agent is contained in an amount of 2 to 6wt% in terms of oxide, based on 100wt% of the total weight of the silica-alumina material.
34. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the carbon precursor solution in the step S2 is one or more of organic acid and alcohol, and the addition amount of the carbon precursor is 5-20wt% of the active metal content.
35. The method for preparing a coal tar hydrogenation catalyst according to claim 5 or 34, wherein the carbon precursor solution in the step S2 is one or more of citric acid, tartaric acid, ethanol and ethylene glycol, and the addition amount of the carbon precursor is 10-20wt% of the active metal content.
36. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the drying temperature in the step S3 is 100-150 ℃ and the drying time is 4-10 h.
37. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the roasting in the step S3 is performed under the condition of a steam-containing gas, wherein the steam-containing gas is a mixture of steam and a carrier gas, and the carrier gas is one or more of nitrogen, helium, neon, argon, krypton and xenon; the volume ratio of the carrier gas to the water vapor is 5: 1-1:2.
38. The method for preparing a coal tar hydrogenation catalyst according to claim 5, wherein the roasting temperature in step S3 is 400-650 ℃.
39. The method for preparing a coal tar hydrogenation catalyst according to claim 5 or 38, wherein the roasting temperature in step S3 is 400-550 ℃.
40. A coal tar hydrogenation process comprising the steps of contacting coal tar with a hydrogen-containing gas in the presence of the coal tar hydrogenation catalyst according to any one of claims 1 to 4 or the coal tar hydrogenation catalyst obtained by the production method according to any one of claims 5 to 39 under hydrogenation reaction conditions.
41. The coal tar hydrogenation process of claim 40, wherein the coal tar is selected from at least one of low temperature coal tar, medium temperature coal tar, and high temperature coal tar.
42. The coal tar hydrogenation process of claim 40, wherein the hydrogenation reaction conditions are: the reaction pressure is 5-20 MPaG, the reaction temperature is 300-420 ℃, and the liquid hourly space velocity is 0.1-1.5 h -1 The volume ratio of the hydrogen oil is 100-1000.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001144A (en) * | 1975-12-19 | 1977-01-04 | Kaiser Aluminum & Chemical Corporation | Process for modifying the pore volume distribution of alumina base catalyst supports |
| US4226743A (en) * | 1979-03-12 | 1980-10-07 | W. R. Grace & Co. | Silica-alumina hydrogel catalyst |
| CN105056928A (en) * | 2015-09-10 | 2015-11-18 | 中国海洋石油总公司 | Preparation method for silicon-aluminium composite oxide with controllable pore structure |
| CN105709789A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Heavy oil hydrocracking catalyst, and preparation method and applications thereof |
| CN108940351A (en) * | 2017-05-26 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of catalysis material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6872685B2 (en) * | 2002-11-08 | 2005-03-29 | Chevron U.S.A. Inc. | Method for preparing a highly homogeneous amorphous silica-alumina composition |
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- 2022-01-11 CN CN202210024872.6A patent/CN114749194B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001144A (en) * | 1975-12-19 | 1977-01-04 | Kaiser Aluminum & Chemical Corporation | Process for modifying the pore volume distribution of alumina base catalyst supports |
| US4226743A (en) * | 1979-03-12 | 1980-10-07 | W. R. Grace & Co. | Silica-alumina hydrogel catalyst |
| CN105709789A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Heavy oil hydrocracking catalyst, and preparation method and applications thereof |
| CN105056928A (en) * | 2015-09-10 | 2015-11-18 | 中国海洋石油总公司 | Preparation method for silicon-aluminium composite oxide with controllable pore structure |
| CN108940351A (en) * | 2017-05-26 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of catalysis material |
Non-Patent Citations (1)
| Title |
|---|
| 双重孔分布氧化铝载体及加氢脱金属催化剂结构与性质研究;季洪海;隋宝宽;凌凤香;张会成;王少军;;石油与天然气化工(第02期);全文 * |
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Effective date of registration: 20231220 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |