CN114749194A - Coal tar hydrogenation catalyst and preparation method thereof - Google Patents
Coal tar hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN114749194A CN114749194A CN202210024872.6A CN202210024872A CN114749194A CN 114749194 A CN114749194 A CN 114749194A CN 202210024872 A CN202210024872 A CN 202210024872A CN 114749194 A CN114749194 A CN 114749194A
- Authority
- CN
- China
- Prior art keywords
- coal tar
- water
- hydrogenation catalyst
- acid
- tar hydrogenation
- 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
- 239000011280 coal tar Substances 0.000 title claims abstract description 135
- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 61
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical group [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 229910001868 water Inorganic materials 0.000 claims abstract description 38
- -1 VIB group metals Chemical class 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 81
- 229910052782 aluminium Inorganic materials 0.000 claims description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 49
- 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
- 238000000034 method Methods 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 27
- 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 26
- 229910052708 sodium Inorganic materials 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 239000007833 carbon precursor 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
- 229920000609 methyl cellulose Polymers 0.000 claims description 8
- 239000001923 methylcellulose Substances 0.000 claims description 8
- 235000010981 methylcellulose Nutrition 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000007524 organic acids Chemical class 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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 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
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical group 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000007787 solid Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001164 aluminium sulphate Substances 0.000 claims description 2
- 235000011128 aluminium sulphate Nutrition 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
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 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
- 239000004411 aluminium Substances 0.000 claims 3
- 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
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000005119 centrifugation Methods 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 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 10
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 10
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 10
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000007935 neutral 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
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- 239000002808 molecular sieve Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008213 purified water Substances 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
- 230000020477 pH reduction Effects 0.000 description 4
- 239000002994 raw material 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
- 230000007547 defect Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 238000009835 boiling Methods 0.000 description 2
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
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- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
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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, and the active metal component is at least one of VIB group metals and/or VIII group metals. The coal tar hydrogenation catalyst provided by the invention has the advantages of high utilization rate of active metals, 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 a coal tar hydrogenation process.
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 by-product obtained from coal in the processes of dry distillation and vaporization, and has an offensive odor, black or blackish brown color, and viscous liquid. Coal tar can be divided into low-temperature coal tar, medium-temperature coal tar and high-temperature coal tar according to the dry distillation 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 unsaturated hydrocarbons such as olefin and polycyclic aromatic hydrocarbon, sulfur and nitrogen compounds, and has the characteristics of high acidity, high colloid content, poor product stability (light stability, storage stability and oxidation stability) and the like, so that a large amount of sulfide and nitride can be generated by direct combustion to cause serious environmental pollution. 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 washing 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 value-added components and high content of low value-added components, is difficult to utilize, and has the defects of complex process flow, more equipment, high energy consumption, serious secondary pollution, poor economic benefit and a plurality of technical defects in the conventional refining process. The coal tar hydrogenation technology is a new exploration and is a main direction for developing a novel coal tar cleaning and utilizing technology; can prolong the industrial chain, improve the resource utilization rate, reduce the pollution and extract products with high added value. The fluidized bed hydrogenation has the advantages of strong raw material adaptability, no bed layer blockage and hot spot problems, stable product property maintenance through online catalyst addition and discharge, long running period and the like, and is very suitable for a coal tar hydrogenation process.
Aiming at the characteristics of high oxygen content, high metal (Fe, Ca) sulfur and nitrogen content and high aromatic hydrocarbon content of the coal tar, particularly 2-4-ring polycyclic aromatic hydrocarbon 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 required to have better cracking performance. Therefore, the development of a coal tar hydrogenation catalyst satisfying the above requirements is an object of research.
CN 201810576449.0A composite catalyst of boiling bed coal tar hydrotreating-hydrocracking and a preparation method thereof. In this patent the composition is made up of MoO in mass percent3、WO3NiO, alumina, a silicon oxide molecular sieve and an auxiliary agent. The patent is that the molecular sieve is directly mixed with the raw materialIn addition, metal and alkaline nitrogen in the coal tar are deposited on the molecular sieve, so that the catalyst is quickly deactivated, the purposes of both hydrotreating and hydrocracking cannot be achieved, and the preparation process of the catalyst is complex.
CN 201310329947.2A coal tar hydrodenitrogenation catalyst 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 accounts for 10wt% -31wt% of the carrier, the alumina accounts for 53wt% -82wt% of the carrier, and the H beta molecular sieve accounts for 8wt% -16wt% of the carrier. The catalyst is easy to vulcanize and has higher activity; the pore structure of the activated carbon is adjustable, which is beneficial to the conversion of colloid components and the removal of nitrogen impurities in the coal tar, thereby slowing down the carbon deposition of the catalyst. The catalyst in the patent can not be directly used as a coal tar raw material, the coal tar can be used only after being subjected to hydrogenation treatment, and the use has certain limitation.
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 utilization rate of active metals, 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, especially for 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 VIB group metals and/or VIII group metals, especially at least one selected from Mo, W, Ni and Co.
In the coal tar hydrogenation catalyst, the content of the VIB group metal is 2-20 wt%, preferably 5-20 wt%, calculated by oxide; the content of the group VIII metal is 1 to 10wt%, preferably 1 to 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 m2A ratio of 150 to 200/g is preferredm2The pore volume 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 the silicon-aluminum material, the forming agent and the binder, and then forming, drying and roasting to obtain a carrier;
s2, preparing an active metal-containing solution, mixing the active metal precursor solution with the carbon precursor solution, and uniformly mixing to obtain the active metal-containing solution;
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.
Further, in the preparation method of 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 methyl cellulose.
Further, in the preparation method of the coal tar hydrogenation catalyst, the binder in step S1 is an organic acid, which may be one or more of acetic acid, citric acid, and the like, and is preferably citric acid.
Further, 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 preparation method of the coal tar hydrogenation catalyst, the calcination in the step S1 is performed in an inert atmosphere, which may be one or more of nitrogen and inert gas, and is preferably nitrogen. The roasting temperature is 500-950 ℃, and preferably 550-900 ℃; the roasting time is 2-6 h.
Further, in the preparation method of the coal tar hydrogenation catalyst, the molding in the step S1 may adopt a molding manner commonly used in the existing catalyst preparation, and the specific molding shape may be selected according to actual needs, such as a sphere, a strip, a clover, etc.
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 method for preparing the 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, and preferably water glass).
Further, in the method for preparing 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 30 wt.% (preferably 15 to 30 wt.%), based on the total weight of the aqueous solution, and its modulus is typically 2.5 to 3.2.
In the method for preparing the 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, particularly a water-soluble inorganic strong acid aluminum salt, more preferably one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, and preferably aluminum sulfate).
Further, in the method for preparing the 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 30-100g/L (preferably 30-80 g/L) based on the total weight of the aqueous solution.
Furthermore, in the method for preparing 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).
Further, in the method for preparing a coal tar hydrogenation catalyst, in order to achieve the technical effects of the present invention more excellently, in particular, in order to obtain a silico-aluminum material with a larger pore volume and a 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 further added to obtain the mixed solution a).
Further, in the method for preparing the 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, and preferably sulfuric acid).
Further, in the method for preparing the coal tar hydrogenation catalyst, the acid is used in the form of an aqueous solution. The acid concentration is 2 to 6wt% (preferably 2 to 5 wt%) based on the total weight of the aqueous solution.
Further, in the method for preparing 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).
Furthermore, in the preparation method of the coal tar hydrogenation catalyst, in the step (1), generally, the aluminum content of the mixed liquid A is 5-20gAl2O3/L calculated as Al2O3, and the silicon content is 5-40gSiO2/L calculated as SiO 2.
Further, in the preparation method of the 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, preferably sodium meta-aluminate).
Further, in the method for preparing the coal tar hydrogenation catalyst, the alkaline aluminum source is used in the form of an aqueous solution. The concentration of the alkaline aluminum source (calculated as Al2O 3) is 130-350g/L (preferably 150-250 g/L) based on the total weight of the aqueous solution, and the caustic ratio is generally 1.15-1.35, preferably 1.15-1.30.
Further, in the method for preparing a coal tar hydrogenation catalyst, the amount of the mixed liquid a is 40 to 70vol% (preferably 40 to 65 vol%) based on the total volume of the mixed liquid a, the alkali aluminum source and the water.
Further, in the method for preparing a coal tar hydrogenation catalyst, the amount of the alkali aluminum source is 20 to 40vol% (preferably 25 to 40 vol%) based on the total volume of the mixed solution a, the alkali aluminum source and water.
Further, in the method for preparing a coal tar hydrogenation catalyst, the amount of water is 10 to 20vol% (preferably 13 to 20 vol%) based on the total volume of the mixed solution a, the alkali aluminum source and water.
Further, in the method for preparing the coal tar hydrogenation catalyst, the mixed solution a and the alkali aluminum source are added to water sequentially or simultaneously (preferably, the mixed solution a and the alkali aluminum source are added to water in a concurrent flow manner).
Furthermore, in the preparation method of the coal tar hydrogenation catalyst, the adding flow rate of the mixed liquid A is 15-50mL/min (preferably 20-40 mL/min).
Further, in the above coal tar hydrogenation catalyst production method, the flow rate of the addition of the alkali 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, and more preferably 8.5 to 10.5).
Further, in the method for preparing a coal tar hydrogenation catalyst, in order to achieve the technical effects of the present invention more excellently, in particular, in order to obtain a silica-alumina material with a larger pore volume, in the step (2), a water-soluble carbonate is further added (preferably, the mixed solution a and the alkaline aluminum source are added to water, and then the water-soluble carbonate is further added to obtain the slurry B).
Further, in the preparation method of the coal tar hydrogenation catalyst, the water-soluble carbonate is selected from one or more carbonates of alkali metals 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 above method for preparing a coal tar hydrogenation catalyst, the water-soluble carbonate is used in the form of a solid.
Further, in the method for preparing the coal tar hydrogenation catalyst, the water-soluble carbonate is added in an amount so that the pH value of the slurry B is 10.5-12 (preferably 11-12).
Further, in the preparation method of 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. Here, the washing may be performed by a washing method conventional in the art, preferably by deionized water, and more preferably at 50 ℃ to 90 ℃. In addition, the separation can adopt one of the means which can realize the separation of liquid-solid two-phase materials in the field, such as filtration, centrifugal separation and the like, and particularly, the separation can adopt a filtration separation mode to obtain solid-phase materials and liquid-phase materials after separation, and the solid-phase materials are 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 100-150 ℃, and the drying time is 6-10 hours.
Further, in the above coal tar hydrogenation catalyst preparation method, in the step (1), the temperature is 25 to 50 ℃ (preferably 25 to 40 ℃), and the pressure is normal pressure.
Further, in the above coal tar hydrogenation catalyst preparation method, in the step (2), the temperature is 50 to 90 ℃ (preferably 50 to 80 ℃), and the pressure is normal pressure.
Further, in the above coal tar hydrogenation catalyst preparation method, in the step (3), the temperature is 180-300 ℃ (preferably 180-280 ℃, more preferably 180-250 ℃), and the pressure is 0.1-0.5MPa (preferably 0.1-0.3 MPa).
Further, in the method for preparing a coal tar hydrogenation catalyst, in order to achieve the technical effects of the present invention more excellently, in the step (3), the hydrothermal treatment time is 0.5 to 15 hours (preferably 0.5 to 12 hours). Furthermore, in the preparation method of the coal tar hydrogenation catalyst, an auxiliary agent, such as one or more of 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). Specific examples of the inorganic salt include a borate, a sulfate, and a nitrate. The amounts of these additives may be arbitrarily adjusted according to the requirements of the subsequent catalyst and the like. In general, these auxiliaries are generally present in a weight amount, calculated as oxides, of from 1 to 8% by weight, preferably from 2 to 6% by weight, relative to 100% by weight of the total weight of the silicoalumina material.
Further, in the preparation method of the coal tar hydrogenation catalyst, in the step S2, the active metal is at least one selected from group VIB metals and/or group VIII metals, and especially at least one selected from Mo, W, Ni, and Co. Further, the active metal precursor may be a Mo-Ni (Co) -P heteropoly acid solution, or Mo (W) -Ni (Co) -NH3·H2O alkaline active metal solution.
Further, in the preparation method of the coal tar hydrogenation catalyst, the carbon precursor solution in step S2 may be one or more of an organic acid and an alcohol. The carbon precursor can be one or more of citric acid, tartaric acid, ethanol and glycol, and the addition amount of the carbon precursor is 5-20 wt% of the active metal content, preferably 10-20 wt%.
Further, in the method for preparing the coal tar hydrogenation catalyst, the carrier obtained in step S1 in step S3 may be mixed with the active metal-containing solution obtained in step S2 by an impregnation method.
Further, 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 h.
Further, in the preparation method of the coal tar hydrogenation catalyst, in the step S3, the calcination is performed under the condition of a water vapor-containing gas, the water vapor-containing gas is a mixed gas of water vapor and a carrier gas, wherein the carrier is one or more of nitrogen, helium, neon, argon, krypton and xenon, and preferably nitrogen. The volume ratio of the carrier to the water vapor is 5: 1-1: 2.
Further, in the preparation method of the coal tar hydrogenation catalyst, the roasting temperature in the step S3 is 400-650 ℃, preferably 400-550 ℃; the roasting time is 3-8 h.
In the third aspect of the invention, coal tar and hydrogen-containing gas are contacted to react 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 can be at least one selected from low-temperature coal tar, medium-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-1The volume ratio of hydrogen to 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 active metal solution is roasted in the inert atmosphere, so that a carbon layer can be formed on the surface of the carrier, the water resistance of the carrier is improved, meanwhile, the carbon layer of the carrier weakens the interaction between the active metal and the carrier in the impregnation process, and meanwhile, the carbonaceous substance in the impregnation liquid is roasted in the atmosphere of nitrogen and water vapor, so that the aggregation of the metal is prevented, 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 method is very suitable for the coal tar hydrogenation process with high oxygen content.
2. In the preparation method of the coal tar hydrogenation catalyst, a silicon source is acidified by an acidic aluminum source and then an inorganic acid in the preparation process of a silicon-aluminum material, cations (sodium ions and the like) enveloped in a ring or cage silicic acid polymer in the silicon source are dissociated, an acidified silica gel group is adsorbed on an aluminum hydroxide colloid, the sodium ions are effectively separated from the silica gel group, and an acidic aluminum solution is added to isolate the dissociated cations, so that the cations (sodium ions) are removed more easily in the follow-up washing process, the difficulty in removing sodium in the follow-up washing process is greatly reduced, and the water consumption for washing is reduced. More importantly, cations (sodium ions) are effectively removed, the acid sites occupied by Na can be recovered, so that the silicon-aluminum material has higher acidity, the obtained silicon-aluminum material has the characteristics of large pore volume, mesoporous-macroporous hierarchical pore canals, high B acid content, high crystallinity, low impurity content (especially low sodium content), good hydrothermal stability and the like, the coal tar hydrogenation catalyst prepared by taking the silicon-aluminum material as the base has the advantages of high utilization rate of active metals, good wear resistance, strong water resistance, high impurity removal rate, high metal containing capacity, good cracking performance and the like, and is suitable for being applied to coal tar hydrogenation, especially to a coal tar hydrogenation process of a boiling bed.
3. In the preparation method of the coal tar hydrogenation catalyst, 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 reaction, the crystal grains of the prepared silicon-aluminum material are promoted to be enlarged, and the silicon-aluminum material with large pore volume and large pore diameter is formed.
4. According to the preparation method of the coal tar hydrogenation catalyst, the pH value of the slurry B is adjusted in the preparation process of the silicon-aluminum material, the slurry system form is changed into a gel-like thixotropic form from the initial flowing state in the high-temperature treatment process, the slurry system form is changed into the flowing state after being treated for a period of time, the silicon-aluminum material and water form a changeable silicon-aluminum-oxygen network structure in the process of changing into the gel-like thixotropic form, and the preparation method of the silicon-aluminum material with large pore volume is facilitated.
Detailed Description
The following detailed description of the embodiments of the present invention is provided by way of specific examples, but it should be noted that the scope of the present 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 silica-alumina materials and catalysts are measured using low temperature nitrogen adsorption. Total acid, B acid and L acid were measured by pyridine infrared adsorption. Sodium oxide and silica were measured using fluorescence analysis. The active metal content was measured spectrophotometrically. The wear index was measured using an air jet method.
All percentages, parts, ratios, etc. referred to within this specification are by weight and pressures are gauge pressures unless explicitly indicated.
In the context of this specification, any two or more embodiments of the invention may be combined in any combination, and the resulting solution is part of the original disclosure of this specification, and is within the scope of the invention.
Example 1
(1) Preparation of silicon-aluminum material
The preparation concentration is 80gAl2O3Aluminum sulfate solution/L and 50gSiO concentration2The silica sol solution with the modulus of 2.8 is used for standby, and the dilute sulphuric acid solution with the concentration of 0.5mol/L is prepared for standby. The caustic ratio is 1.15, the concentration is 180 gAl2O3and/L of sodium metaaluminate solution for later use.
1.0L of 50gSiO in concentration was measured2Adding the silica sol solution into a container, and slowly adding 0.8L of 80gAl under stirring2O3Aluminum sulfate solution/L, during which aluminum hydroxide colloids are formed, but the solution is still in liquid form. Then adding 1mol/L dilute sulfuric acid solution, adjusting the pH value to 3.5, and completing acidification treatment to obtain mixed liquor A.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding the mixed solution A into the reactor at a rate of 20mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the amount of sodium metaaluminate is 640mL, and 41g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor, and is treated for 2 hours under the condition of stirring at the treatment temperature of 210 ℃ and the treatment pressure of 0.2 MPa. Washing the treated slurry with hot water of 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a dried sample PO-1, and roasting at 600 ℃ for 5h to obtain the silicon-aluminum material P-1, wherein the properties of the silicon-aluminum material P-1 are shown in Table 1.
(2) Preparation of hydrogenation catalyst
Taking 500g of prepared PO-1 silicon-aluminum dry sample, adding 8.2g of methyl cellulose, 11.96g of citric acid and 470g of purified water, mixing uniformly, and then forming spheres. The sample was dried at 130 ℃ for 5h and then calcined at 800 ℃ under a nitrogen atmosphere for 4h to give a support Z1 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 molybdenum oxide and the basic nickel carbonate are completely dissolved. Then, 30.93g of citric acid was added thereto and dissolved by stirring, and the solution was made to a volume of 2000mL with distilled water to obtain a solution L1.
The support Z1 was saturated with the solution L1 and dried at 110 ℃ for 2 h. In a volume ratio of nitrogen to water vapor of 3: calcining at 1 and 450 ℃ for 3h to obtain the catalyst C1, and the specific properties are shown in Table 2.
Example 2
The other conditions were the same as in example 1 except that: changing the silica sol into a water glass solution, changing the adding amount of water at the bottom of the reactor into 800ml, controlling the pH value of the reaction to be 8.5, obtaining a silicon-aluminum material dry sample PO-2, roasting at 600 ℃ for 5h, and obtaining a silicon-aluminum material P-2, wherein the properties of the material are shown in Table 1.
And taking 500g of prepared PO-2 silicon-aluminum dry sample, adding 5.14g of corn starch, 9.85g of acetic acid (85 wt%) and 480g of water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 700 ℃ for 5 hours to obtain a carrier Z2 with the particle size of 0.7-1.2 mm.
The support Z2 was saturated with the solution L1 and dried at 110 ℃ for 2 h. In the volume ratio of nitrogen to water vapor of 2: calcining at 1 and 500 ℃ for 4h to obtain the catalyst C2, and 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 70SiO2Adding 1mol/L dilute sulfuric acid solution, adjusting the pH value to 4.0, adding the mixed solution A at 25mL/min, treating at 250 ℃ under the treatment pressure of 0.4MPa for 4h to obtain a silicon-aluminum material dry sample PO-3, and roasting at 600 ℃ for 5h to obtain a silicon-aluminum material P-3, wherein the properties of the material are shown in Table 1.
And taking 500g of prepared PO-3 silicon-aluminum dry sample, adding 6.15g of methyl cellulose, 12.42g of tartaric acid and 460g of water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 650 ℃ for 4 hours to obtain a carrier Z3 with the particle size of 0.7-1.2 mm.
The support Z3 was saturated with the solution L1 and dried at 110 ℃ for 2 h. In the volume ratio of nitrogen to water vapor of 1: calcining at 1 and 480 ℃ for 3h to obtain the catalyst C3, wherein the specific properties are shown in Table 2.
Example 4
(1) Preparation of silicon-aluminum material
The preparation concentration is 30gAl2O3Aluminum sulfate solution/L and a concentration of 60gSiO2The silica sol solution with the modulus of 2.8 is used for standby, and the dilute nitric acid solution with the concentration of 1.5mol/L is prepared for standby. The caustic ratio is 1.20, the concentration is 150 gAl 2O3and/L of sodium metaaluminate solution for later use.
1.5L of the solution with the concentration of 60gSiO is measured2Adding the/L silica sol solution into a container, and slowly adding 1.0L of 30gAl under stirring2O3Aluminum sulfate solution/L, during which aluminum hydroxide colloids are formed, but the solution is still in liquid form. Then 1.5mol/L dilute nitric acid is added to adjust the pH value to 3.0, and the acidification treatment is finished to obtain mixed liquor A.
Adding 800mL of deionized water serving as bottom water into a 5000mL reactor, starting stirring and heating, heating the deionized water to 70 ℃, adding the mixed solution A into the reactor at a rate of 15mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 8.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the dosage of sodium metaaluminate is 690mL, and 72g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.0. The slurry is put into a reactor and is treated for 3 hours under the condition of stirring at the treatment temperature of 250 ℃ and the treatment pressure of 0.3 MPa. Washing the treated slurry with hot water of 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a dried sample PO-4, and roasting at 600 ℃ for 5h to obtain the silicon-aluminum material P-4, wherein the properties of the silicon-aluminum material P-4 are shown in Table 1.
(2) Preparation of hydrogenation catalyst
Taking 500g of prepared PO-4 silicon-aluminum dry sample, adding 7.00g of wheat starch, 12.35g of acetic acid (85%) and 490g of purified water, mixing uniformly, and then forming into spheres. The sample was dried at 130 ℃ for 5h and then calcined at 750 ℃ for 3h under a nitrogen atmosphere to give a support Z4 with a particle size of 0.7-1.2 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 molybdenum oxide and the basic nickel carbonate are completely dissolved. Then, 39.45g of ethylene glycol was added thereto and dissolved by stirring, and the solution was made to 1000mL with distilled water to obtain a solution L2.
The support Z4 was saturated with the solution L2 and dried at 110 ℃ for 2 h. In the volume ratio of nitrogen to water vapor of 1: calcining at 600 deg.C for 3h to obtain catalyst C4, with specific properties shown in Table 2.
Example 5
The other conditions were the same as in example 4 except that: the silica sol solution is changed into water glass, and the concentration is changed into 50SiO2and/L, adding the mixed solution A at a rate of 25mL/min instead, treating at 210 ℃ under a treatment pressure of 0.4MPa for 4h to obtain a silicon-aluminum material dry sample PO-5, and roasting at 600 ℃ for 5h to obtain a silicon-aluminum material P-5, wherein the properties of the material are shown in Table 1.
And taking 500g of prepared PO-5 silicon-aluminum dry sample, adding 8.23g of methyl cellulose, 10.15g of citric acid and 500g of water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 700 ℃ for 4 hours to obtain a carrier Z5 with the particle size of 0.7-1.2 mm.
The support Z5 was saturated with the solution L2 and dried at 110 ℃ for 2 h. In the volume ratio of nitrogen to water vapor of 1: 2, roasting at 450 ℃ for 4 hours to obtain the catalyst C5, wherein the specific properties are shown in Table 2.
Comparative example 1
(1) Preparation of silicon-aluminum material
The preparation concentration is 80gAl2O3Aluminum sulfate solution/L and 50gSiO concentration2The silica sol solution with the modulus of 2.8 is ready for use. The caustic ratio was 1.15, and the concentration was 180 gAl2O3and/L of sodium metaaluminate solution for later use.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding aluminum sulfate into the reactor at 20mL/min and 30mL/min of silica sol, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature of slurry in the reactor and the pH value constant. After the reaction is finished, the amount of sodium metaaluminate is 640mL, and 41g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor, and is treated for 2 hours under the condition of stirring at the treatment temperature of 210 ℃ and the treatment pressure of 0.2 MPa. Washing the treated slurry with hot water at 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a dried sample PFO-1, and roasting at 600 ℃ for 5h to obtain a silicon-aluminum material PF-1, wherein the properties of the silicon-aluminum material are shown in Table 1.
(2) Preparation of hydrogenation catalyst
And taking 500g of prepared PO-1 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 sphere. The sample was dried at 130 ℃ for 5 h and then calcined at 800 ℃ for 4h under nitrogen atmosphere to give the carrier ZF1 with 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 molybdenum oxide and the basic nickel carbonate are completely dissolved. Then, 30.93g of citric acid was added thereto and dissolved by stirring, and the solution was made up to 2000mL with distilled water to obtain a solution L1.
The carrier ZF1 was saturated with solution L1 and dried at 110 ℃ for 2 h. Calcining at 450 deg.C for 3h under nitrogen atmosphere to obtain catalyst CF1 with specific properties shown in Table 2.
Comparative example 2
(1) Preparation of silicon-aluminum material
The preparation concentration is 80gAl2O3L of aluminium sulphate solution and concentrateDegree of 50gSiO2The silica sol solution with the modulus of 2.8 is used for standby, and the dilute sulphuric acid solution with the concentration of 0.5mol/L is prepared for standby. The caustic ratio is 1.15, the concentration is 180 gAl2O3and/L of sodium metaaluminate solution for later use.
0.8L of 80gAl in concentration is measured2O3Adding the aluminum sulfate solution into a container, slowly adding 1.0L of 50gSiO solution under stirring 2The process of the sol solution of/L generates a large amount of aluminum hydroxide gel, and the fluidity is poor. Then adding 1mol/L dilute sulfuric acid solution, adjusting the pH value to 3.5, and completing acidification treatment to obtain mixed liquor A.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding the mixed solution A into the reactor at a rate of 20mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the amount of sodium metaaluminate is 640mL, and 41g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor, and is treated for 2 hours under the condition of stirring at the treatment temperature of 210 ℃ and the treatment pressure of 0.2 MPa. Washing the treated slurry with hot water at 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a dried sample PFO-2, and roasting at 600 ℃ for 5h to obtain a silicon-aluminum material PF-2, wherein the properties of the silicon-aluminum material are shown in Table 1.
(2) Preparation of hydrogenation catalyst
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, mixing uniformly and then forming a sphere. The sample was dried at 130 ℃ for 5h and then calcined at 800 ℃ for 4h under nitrogen atmosphere to give the carrier ZF2 with 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 molybdenum oxide and the basic nickel carbonate are completely dissolved. Then, 30.93g of citric acid was added thereto and dissolved by stirring, and the solution was made to a volume of 2000mL with distilled water to obtain a solution L1.
The carrier ZF2 was saturated with the solution L1 and dried at 110 ℃ for 2 h. Calcining at 450 deg.C for 3h under nitrogen atmosphere to obtain catalyst CF2 with specific properties shown in Table 2.
Comparative example 3
(1) Preparation of silicon-aluminum material
The preparation concentration is 80gAl2O3Aluminum sulfate solution/L and 50gSiO concentration2The silica sol solution with the modulus of 2.8 is used for standby, and the dilute sulphuric acid solution with the concentration of 0.5mol/L is prepared for standby. The caustic ratio is 1.15, the concentration is 180 gAl2O3and/L of sodium metaaluminate solution for later use.
1.0L of 50gSiO in concentration was measured2Adding the silica sol solution into a container, and slowly adding 0.8L of 80gAl under stirring2O3Aluminum sulfate solution/L, during which aluminum hydroxide colloids are formed, but the solution is still in liquid form. Then adding 1mol/L dilute sulfuric acid solution, adjusting the pH value to 3.5, and completing acidification treatment to obtain mixed liquor A.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding the mixed solution A into the reactor at a rate of 20mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the using amount of sodium metaaluminate is 640 mL.
Washing the reacted slurry with hot water at 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a dried sample PFO-3, and roasting at 600 ℃ for 5h to obtain a silicon-aluminum material PF-3, wherein the properties of the silicon-aluminum material are shown in Table 1.
(2) Preparation of hydrogenation catalyst
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, mixing uniformly and then forming a sphere. The sample was dried at 130 ℃ for 5h and then calcined at 800 ℃ under nitrogen atmosphere for 4h to give the carrier ZF3 with 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 molybdenum oxide and the basic nickel carbonate are completely dissolved. Then, 30.93g of citric acid was added thereto and dissolved by stirring, and the solution was made up to 2000mL with distilled water to obtain a solution L1.
The carrier ZF3 was saturated with solution L1 and dried at 110 ℃ for 2 h. Calcining at 450 deg.C for 3h under nitrogen atmosphere to obtain catalyst CF3 with specific properties shown in Table 2.
TABLE 1 Properties of the Si-Al materials
TABLE 2 Properties of the catalysts
The catalyst is subjected to activity evaluation on a continuous tank reactor (CSTR) device, medium-low temperature coal tar is adopted for evaluation, and the properties and evaluation conditions of the medium-low temperature coal tar are shown in Table 3. The oil produced after 1000h running was sampled and analyzed, and the activity of comparative example 3 was taken as 100, and the results of other evaluations compared with the activity of comparative example 3 are shown in Table 4.
TABLE 3 Properties and evaluation conditions of Medium-Low temperature coal tar
TABLE 4 evaluation results of catalysts
As can be seen from the data in the tables: 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 a 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, effectively converts medium and low temperature coal tar, and provides a high-quality raw material for subsequent product processing.
Claims (24)
1. A coal tar hydrogenation 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 group metal and/or VIII group metal, especially at least one selected from Mo, W, Ni and Co.
2. The coal tar hydrogenation catalyst according to claim 1, wherein the group VIB metal is present in an amount of 2 to 20 wt.%, preferably 5 to 20 wt.%, calculated as oxide; the content of the group VIII metal is 1 to 10wt%, preferably 1 to 6wt%, in terms of oxide.
3. The coal tar hydrogenation catalyst of claim 1, wherein the catalyst has the following specific properties: the specific surface area is 120-220 m 2A preferred concentration is 150 to 200 m2The pore volume is 0.4-0.8 mL/g, preferably 0.5-0.75 mL/g, the total acid number 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.
4. A preparation method of a coal tar hydrogenation catalyst comprises the following steps:
s1, under the contact condition, uniformly mixing the silicon-aluminum material, the forming agent and the binder, and then forming, drying and roasting to obtain a carrier;
s2, preparing an active metal-containing solution, mixing the active metal precursor solution with the carbon precursor solution, and uniformly mixing to obtain the active metal-containing solution;
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.
5. The method for preparing the coal tar hydrogenation catalyst according to claim 4, wherein the forming agent in the step S1 is one or more of cellulose and starch, preferably cellulose and more preferably methyl cellulose.
6. The method for preparing the coal tar hydrogenation catalyst according to claim 4, wherein the binder in the step S1 is an organic acid selected from one or more of acetic acid and citric acid, preferably citric acid.
7. The preparation method of the coal tar hydrogenation catalyst according to claim 4, wherein the drying temperature in the step S1 is 100-150 ℃.
8. The method for preparing the coal tar hydrogenation catalyst according to claim 4, wherein the calcination in the step S1 is performed under an inert atmosphere, wherein the inert atmosphere is one or more of nitrogen and inert gas, and is preferably nitrogen; the roasting temperature is 500-950 ℃, and preferably 550-900 ℃.
9. The method for preparing the coal tar hydrogenation catalyst according to claim 4, wherein the silicon-aluminum material in the step S1 is prepared by the following method:
(1) adding an acid 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.
10. The method for preparing the coal tar hydrogenation catalyst according to claim 9, wherein 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), and/or the silicon source is used in the form of an aqueous solution, and the concentration of the silicon source (calculated as SiO 2) is 5-30wt% (preferably 15-30 wt%) and the modulus is 2.5-3.2, based on the total weight of the aqueous solution, and/or the acidic aluminum source is a water-soluble acidic aluminum-containing compound (preferably a water-soluble acidic inorganic aluminum-containing compound, particularly a water-soluble inorganic strong acid aluminum salt, more preferably one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, preferably aluminium sulphate) and/or the source of acidic aluminium is used in the form of an aqueous solution and the concentration of the source of acidic aluminium (calculated as Al2O 3) is 30-100g/L (preferably 30-80 g/L) based on the total weight of the aqueous solution and/or the weight ratio of the source of silicon (calculated as SiO 2) to the source of acidic aluminium (calculated as Al2O 3) is 1:1-9:1 (preferably 1:1-7: 1).
11. The method for preparing a coal tar hydrogenation catalyst according to claim 9, wherein in 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), and/or 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, and preferably, sulfuric acid), and/or the acid is used in the form of an aqueous solution, and the concentration of the acid is 2-6wt% (preferably, 2-5 wt%) based on the total weight of the aqueous solution, and/or the acid is added in an amount such that the pH of the mixed solution a is 2-4 (preferably, 3-4).
12. The preparation method of the coal tar hydrogenation catalyst according to claim 9, wherein 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, particularly an alkali metaaluminate, more preferably one or more selected from sodium metaaluminate and potassium metaaluminate, preferably sodium metaaluminate), and/or the alkaline aluminum source is used in the form of an aqueous solution, and the concentration of the alkaline aluminum source (calculated as Al2O 3) is 130-350g/L (preferably 150-250 g/L) based on the total weight of the aqueous solution, the causticity ratio is 1.15-1.35, preferably 1.15-1.3, and/or the mixed solution A is used in an amount of 40-70vol% (preferably 40-65%) based on the total volume of the mixed solution A, the alkaline aluminum source and water, and/or the amount of the alkaline aluminum source is 20-40vol% (preferably 25-40 vol%) based on the total volume of the mixed liquid a, the alkaline aluminum source and water, and/or the amount of the water is 10-20vol% (preferably 13-20 vol%) based on the total volume of the mixed liquid a, the alkaline aluminum source and water, and/or the mixed liquid a and the alkaline aluminum source are added to water sequentially or simultaneously (preferably the mixed liquid a and the alkaline aluminum source are added to water in a concurrent manner), and/or the added flow rate of the mixed liquid a is 15-50mL/min (preferably 20-40 mL/min), and/or the added 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 (preferably 8.0-10.5, more preferably 8.5 to 10.5).
13. The method for preparing a coal tar hydrogenation catalyst according to claim 9, wherein in step (2), a water-soluble carbonate is further added (preferably, the mixture a and the alkaline aluminum source are added to water, and then the water-soluble carbonate is added to obtain the slurry B), and/or the water-soluble carbonate is selected from carbonates of one or more of alkali metals and ammonium (preferably, one or more selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate, preferably sodium carbonate), and/or the water-soluble carbonate is used in the form of a solid, and/or the water-soluble carbonate is added in an amount such that the pH of the slurry B is 10.5 to 12 (preferably, 11 to 12).
14. The coal tar hydrogenation catalyst preparation method according to claim 9, wherein in step (3), the silica-alumina material is separated from the hydrothermally treated reaction system (such as by filtration or centrifugation), washed to neutrality, and then dried, and/or the drying conditions include: the drying temperature is 100-150 ℃, and the drying time is 6-10 hours.
15. The method for preparing a coal tar hydrogenation catalyst according to claim 9, wherein in the step (1), the temperature is 25-50 ℃ (preferably 25-40 ℃) and the pressure is normal pressure, and/or, in the step (2), the temperature is 50-90 ℃ (preferably 50-80 ℃) and the pressure is normal pressure, and/or, in the step (3), the temperature is 180-.
16. The method for preparing a coal tar hydrogenation catalyst according to claim 9, wherein an auxiliary agent (preferably one or more selected from phosphorus, boron and titanium) is further added, and/or the auxiliary agent is contained in an amount of 1-8wt% (preferably 2-6 wt%) by weight calculated on oxide basis, relative to 100wt% of the total weight of the silicon-aluminum material.
17. The method for preparing the coal tar hydrogenation catalyst according to claim 4, wherein the active metal in step S2 is at least one selected from VIB group metals and/or VIII group metals, especially at least one selected from Mo, W, Ni and Co.
18. The preparation method of the coal tar hydrogenation catalyst according to claim 4, wherein the carbon precursor solution in the step S2 is one or more of organic acid and alcohol, specifically one or more of citric acid, tartaric acid, ethanol and ethylene glycol, and the addition amount of the carbon precursor is 5-20 wt%, preferably 10-20 wt% of the active metal content.
19. The preparation method of the coal tar hydrogenation catalyst according to claim 4, wherein the drying temperature in the step S3 is 100-150 ℃, and the drying time is 4-10 h.
20. The method for preparing the coal tar hydrogenation catalyst according to claim 4, wherein the calcination in the step S3 is performed under the condition of water vapor-containing gas, the water vapor-containing gas is a mixed gas of water vapor and a carrier gas, the carrier gas is one or more of nitrogen, helium, neon, argon, krypton and xenon, and is preferably nitrogen; the volume ratio of the carrier to the water vapor is 5: 1-1: 2.
21. The method for preparing the coal tar hydrogenation catalyst according to claim 4, wherein the calcination temperature in step S3 is 400-650 ℃, preferably 400-550 ℃.
22. A coal tar hydrogenation process, wherein coal tar and hydrogen-containing gas are contacted to react under hydrogenation reaction conditions in the presence of the coal tar hydrogenation catalyst of any one of claims 1 to 3 or the coal tar hydrogenation catalyst obtained by the preparation method of any one of claims 4 to 21.
23. The coal tar hydrogenation process according to claim 22, wherein the coal tar material is selected from at least one of low temperature coal tar, medium and low temperature coal tar, medium temperature coal tar, and high temperature coal tar.
24. The coal tar hydrogenation process according to claim 22, 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-1The volume ratio of hydrogen to oil is 100-1000.
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