CN113797941B - Catalytic material with hydrogenation performance and preparation method and application thereof - Google Patents
Catalytic material with hydrogenation performance and preparation method and application thereof Download PDFInfo
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- CN113797941B CN113797941B CN202010527138.2A CN202010527138A CN113797941B CN 113797941 B CN113797941 B CN 113797941B CN 202010527138 A CN202010527138 A CN 202010527138A CN 113797941 B CN113797941 B CN 113797941B
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- catalytic material
- hydrogenation
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- preparing
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 74
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000002006 petroleum coke Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 235000011181 potassium carbonates Nutrition 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002994 raw material Substances 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
- 239000000706 filtrate Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000006012 monoammonium phosphate Substances 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229910052786 argon Inorganic materials 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 229960003563 calcium carbonate Drugs 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 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
- 229910052742 iron Inorganic materials 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
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 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
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000003054 catalyst Substances 0.000 abstract description 59
- 230000000694 effects Effects 0.000 abstract description 14
- 238000011156 evaluation Methods 0.000 description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 9
- 229910018104 Ni-P Inorganic materials 0.000 description 8
- 229910018536 Ni—P Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 8
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015621 MoO Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- -1 one or more of Zr Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a catalytic material with hydrogenation performance, a preparation method and application thereof, wherein the catalytic material takes petroleum coke-based activated carbon as a carrier, and has larger specific surface area, pore volume and pore diameter. The preparation method comprises the following steps: (1) Mixing petroleum coke, a pore-enlarging agent and an auxiliary agent, and contacting with water vapor for treatment after uniform mixing; (2) Mixing the sample obtained in the step (1) with an acid solution, and further washing and drying to obtain a carrier; (3) Preparing an aqueous solution containing a hydrogenation metal component and P from a compound containing the hydrogenation metal component, a phosphorus-containing compound and water; (4) Mixing the aqueous solution obtained in the step (3) with the carrier obtained in the step (2), standing, drying and roasting to obtain the catalytic material. The catalyst material has higher hydrogenation activity, and the catalyst has high metal capacity and better stability.
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 catalytic material with hydrogenation performance and a preparation method thereof.
Background
At present, from the primary energy consumption trend of China and worldwide, petroleum is still used as the main energy source of the world for a long time. With the sustainable development of the economy of China, the petroleum demand is increased year by year, although the petroleum yield of China is gradually increased, when the actual demand still cannot be met, the net import amount of the petroleum of China is increased year by year, the external dependence is over 70%, and for large petroleum importation households like medium petrochemical industry, the external dependence is higher. Residuum is the highest impurity content, heaviest component of petroleum and difficult to process. Along with the gradual heavy and poor quality of imported petroleum in China, how to fully utilize residual oil resources in petroleum is a key for solving the energy problem and improving the energy utilization efficiency. The residuum hydrogenation technology has become a core technology for processing residuum in various refineries by virtue of the advantages of high product quality, high profit, environmental protection and the like, wherein the catalyst becomes a core in the residuum hydrogenation technology.
CN105983413B discloses a preparation method of a high-activity residuum hydrogenation catalyst. The catalyst prepared is prepared by Al 2 O 3 Is a carrier and contains rare earth metal oxide and active metal oxide. The rare earth metal oxide and the active metal oxide are distributed at intervals on the catalyst, so that the dispersion performance of the active components is improved, and the activity of the catalyst is improved.
CN108421561a discloses a heavy oil hydrogenation catalyst, a preparation method thereof and a heavy oil hydrotreating method. The preparation method comprises the steps of firstly loading a water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst; then, the solution containing the organic complexing agent is used as impregnating solution, the semi-finished catalyst is impregnated, and then the catalyst is obtained after drying and without roasting. When the catalyst is used for heavy oil hydrotreatment, higher demetallization rate, carbon residue removal rate and desulfurization rate can be obtained.
According to the preparation method of the catalyst disclosed by the patent, the carrier is modified by adding the auxiliary agent, so that the dispersion performance of the active metal on the carrier is improved, and the activity of the catalyst is improved. However, the above patent mostly adopts alumina as a carrier, and the effect of the modified alumina on active metal is still strong, thus preventing the further improvement of the activity of the catalyst; meanwhile, the heavy oil hydrogenation catalyst using alumina as a carrier is changed into dangerous waste after operation, and the waste catalyst has complicated treatment and recycling steps and high cost, and is unfavorable for the wide application of the catalyst.
Disclosure of Invention
In order to overcome the defects existing in the prior art, the invention aims to provide a catalytic material with hydrogenation performance, a preparation method and application thereof, wherein the catalytic material takes petroleum coke-based active carbon as a carrier, has larger specific surface area, pore volume and pore diameter, is beneficial to the dispersion of active metal components, weakens interaction with the active components to enable the active components to be easier to vulcanize, is easy to form more hydrogenation active centers, enables the catalytic material to have higher hydrogenation activity, and has high metal capacity and better stability compared with the conventional oxide carrier adopted in the prior art.
The first aspect of the invention provides a preparation method of a catalytic material with hydrogenation performance, which comprises the following steps:
(1) Mixing petroleum coke, a pore-enlarging agent and an auxiliary agent, and contacting with water vapor for treatment after uniform mixing;
(2) Mixing the sample obtained in the step (1) with an acid solution, and further washing and drying to obtain a carrier;
(3) Preparing an aqueous solution containing a hydrogenation metal component and P from a compound containing the hydrogenation metal component, a phosphorus-containing compound and water;
(4) Mixing the aqueous solution obtained in the step (3) with the carrier obtained in the step (2), standing, drying and roasting to obtain the catalytic material.
In the preparation method of the catalytic material with hydrogenation performance, the pore-expanding agent in the step (1) may be one or more of calcium carbonate, calcium acetate, magnesium carbonate and magnesium acetate, and is preferably calcium carbonate.
In the preparation method of the catalytic material with hydrogenation performance, the auxiliary agent in the step (1) can be one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium oxalate and sodium oxalate, and is preferably potassium carbonate.
In the preparation method of the catalytic material with hydrogenation performance, the weight ratio of petroleum coke, pore expanding agent and auxiliary agent in the step (1) is 1:0.02 to 0.20:1 to 7, preferably 1:0.05 to 0.15:2 to 6.
In the preparation method of the catalytic material with hydrogenation performance, the mass space velocity of the water vapor in the step (1) is 10-100 h -1 Preferably 20 to 80. 80h -1 . The mass airspeed of the water vapor is the ratio of the mass of the deionized water to the mass of the petroleum coke which is introduced per hour.
In the preparation method of the catalytic material with hydrogenation performance, the specific process of the treatment in the step (1) is as follows: the petroleum coke, the pore-enlarging agent and the auxiliary agent are uniformly mixed, and then the temperature is raised in the steam atmosphere, wherein the treatment temperature is 500-1000 ℃, preferably 600-900 ℃, and the treatment time is 30-240 min, preferably 60-180 min. The treatment process further preferably comprises two stages, wherein the first stage is carried out at 500-800 ℃, preferably 600-800 ℃ for 15-120 min, and the second stage is carried out at a temperature of 800-1000 ℃ for 15-120 min.
In the preparation method of the catalytic material with hydrogenation performance, the acid solution in the step (2) is an inorganic acid solution, and specifically may be one or more of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid. The concentration of the acid solution is 10-30wt%. The volume ratio of the acid solution to the sample obtained in the step (1) is 1:1-10:1, and the mixing time is 4-14 h, preferably 6-12 h.
In the preparation method of the catalytic material with hydrogenation performance, the washing in the step (2) is water washing, firstly, the sample is mixed with deionized water, and solid-liquid separation is carried out after uniform mixing until the pH value of the filtrate is neutral. The mass ratio of the sample to the deionized water is 1:5-1:30, preferably 1:10-1:20.
In the preparation method of the catalytic material with hydrogenation performance, the drying temperature in the step (2) is 100-200 ℃, preferably 120-180 ℃, the drying time is 2-10 h, preferably 4-8 h; the drying is preferably carried out under vacuum.
In the preparation method of the catalytic material with hydrogenation performance, the compound containing the hydrogenation metal component in the step (3) is a compound containing VIB metal and/or VIII metal, the compound containing VIB metal can be one or more of molybdenum-containing compounds and tungsten-containing compounds, and the compound containing VIII metal is one or more of nickel-containing compounds and cobalt-containing compounds. The molybdenum-containing compound may be molybdenum oxide and/or ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate and/or nickel nitrate; the cobalt-containing compound is basic cobalt carbonate and/or cobalt nitrate.
In the preparation method of the catalytic material with hydrogenation performance, the phosphorus-containing compound in the step (3) may be one or more of phosphoric acid, monoammonium phosphate and monoammonium phosphate.
In the preparation method of the catalytic material with hydrogenation performance, the concentration of the hydrogenation metal component in the aqueous solution containing the hydrogenation metal component and P in the step (3) is 0.03-0.5 g/mL (calculated by hydrogenation metal oxide), and the concentration of P is 0.002-0.05 g/mL. The formulation may be carried out using methods known in the art.
In the preparation method of the catalytic material with hydrogenation performance, the standing time in the step (4) is 1-3 h.
In the preparation method of the catalytic material with hydrogenation performance, the drying temperature in the step (4) is 80-120 ℃ and the drying time is 4-12 h.
In the preparation method of the catalytic material with hydrogenation performance, the roasting in the step (4) is performed under an inert atmosphere, wherein the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton and xenon; the roasting temperature is 400-600 ℃, and the roasting time is 1-5 h.
In the preparation method of the catalytic material with hydrogenation performance, one or more of other metals, such as Fe, zr, ti, B, la, ce, can be introduced on the catalyst carrier obtained in the step (2).
The second aspect of the invention provides a catalytic material with hydrogenation performance obtained by the preparation method.
The catalytic material with hydrogenation performance comprises a hydrogenation active metal component and a carrier, wherein the hydrogenation active metal component is one or more of VIB group metal and/or VIII group metal, and the carrier is petroleum coke-based active carbon.
In the catalytic material with hydrogenation performance, an auxiliary agent is introduced into the catalytic material with hydrogenation performance, and the auxiliary agent is one or more of P, zr, ti, fe. The content of the auxiliary agent (calculated as oxide) is 0.1-10wt% based on the weight of the catalyst.
In the catalytic material with hydrogenation performance, the group VIB metal is Mo and/or W, and the group VIII metal is Ni and/or Co.
In the catalytic material with hydrogenation performance, the metal component is preferably Mo and Ni, and MoO is based on the weight of the catalyst 3 The content is 2-30wt% and the NiO content is 1-15wt%.
In the above catalytic materials with hydrogenation properties, other metals, such as one or more of Zr, ti, B, la, ce, may be incorporated into the support.
In the catalytic material with hydrogenation performance, the catalytic material with hydrogenation performance has the following properties: the specific surface area is 400-800 m 2 Per g, pore volume is 2.0-4.0 mL/g.
In a third aspect, the present invention provides a process for hydrotreating a hydrocarbonaceous feedstock, wherein the hydrocarbonaceous feedstock is mixed with hydrogen and reacted in a reaction system, wherein the reaction system is filled with the catalytic material having hydrogenation properties as described above.
In the above-mentioned hydrocarbon-containing raw material hydrotreating process, the hydrocarbon-containing raw material may be one or several of diesel oil, wax oil and residual oil, in which the hydrocarbon raw material is preferably residual oil.
In the hydrocarbon-containing raw material hydrotreating process, the reaction conditions are as follows: the reaction temperature is 320-450 ℃, the reaction pressure is 6-18 MPa, the volume ratio of hydrogen to oil is 400-1000:1, and the volume airspeed is 0.1-3.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the reaction temperature is 340-430 DEG CThe reaction pressure is 8-15 MPa, the hydrogen-oil volume ratio is 500-800:1, and the volume airspeed is 0.2-2.0 h -1 。
Compared with the prior art, the catalytic material with hydrogenation performance, and the preparation method and application thereof have the following advantages:
1. in the preparation method of the catalytic material with hydrogenation performance, the pore-expanding agent can be decomposed to generate oxide and carbon dioxide with through holes and pore-expanding effect in the petroleum coke treatment process, the generated oxide further reacts with an auxiliary agent in a water vapor atmosphere to generate the pore-expanding agent again, and meanwhile, the strong base activator (potassium hydroxide and sodium hydroxide) is obtained. The regenerated pore-expanding agent continues to perform pore-expanding treatment on the petroleum coke, and the byproduct strong base (potassium hydroxide and sodium hydroxide) has a high activation effect on the petroleum coke, so that the petroleum coke can be activated in the treatment process, and the auxiliary agent can repeatedly react until the auxiliary agent is completely reacted. The continuously generated carbon dioxide can lead the active carbon carrier to have larger pore volume and pore diameter, is beneficial to the approaching, diffusion and conversion of macromolecules such as asphaltene and the like in the heavy oil and active centers, and has higher holding capacity for impurities in the heavy oil raw material; meanwhile, oxide generated by decomposing the pore-expanding agent can be removed by acid washing, and the property of the activated carbon carrier is not affected.
2. In the preparation method of the catalytic material with hydrogenation performance, in the treatment process of the step (1), water vapor mainly reacts with oxide generated by the pore-expanding agent, so that the pore-expanding agent is continuously regenerated on one hand, and a strong base activator with high activation capability for petroleum coke is generated on the other hand, and the strong base is not directly added for activation; when the pore-expanding agent is reacted, steam is continuously introduced, the steam can continuously activate the petroleum coke, and the pore-expanding agent can play roles of re-opening and pore expanding, so that the activated carbon carrier has larger pore volume and pore diameter.
3. Compared with the conventional oxide carrier adopted in the prior art, the catalytic material with hydrogenation performance has larger specific surface area and pore volume, can load enough active metal components, is favorable for the dispersion of the active metal components, ensures that the interaction between the carrier and the active metal components is weaker, ensures that the active metal is vulcanized more completely, is easy to form more hydrogenation active centers, and ensures that the catalytic material has higher hydrogenation activity.
4. The catalytic material with hydrogenation performance takes the petroleum coke-based active carbon as the carrier, and can effectively disperse coke precursor, terminate free radical reaction, reduce reaction coke formation and improve the carbon deposition resistance of the catalyst by utilizing the compatibility of the active carbon carrier and carbon deposition generated in the application process.
5. The catalytic material with hydrogenation performance takes the petroleum coke-based active carbon as a carrier, is favorable for recycling the active metal, simplifies the recycling process of the active metal in the waste agent, and reduces secondary pollution to the environment.
Detailed Description
The following further illustrates the aspects and effects of the present invention by way of specific examples. In the invention, the weight percent is the mass fraction.
The specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen physical adsorption method, and are specifically measured by adopting a low-temperature nitrogen adsorption instrument of ASAP2420 model of America microphone company. The specific process comprises the following steps: and (3) taking a small amount of samples, carrying out vacuum treatment for 3-4 hours at 300 ℃, and finally, placing the products under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen adsorption-desorption test. Wherein the surface area is obtained according to the BET equation and the pore size distribution is obtained according to the BJH model.
Example 1
(1) Carrier preparation
1000g of petroleum coke Jiao Yanmo to powder, 50g of calcium carbonate and 3000g of potassium carbonate are evenly mixed, placed in a tube furnace, heated, and after the temperature exceeds 100 ℃, steam is introduced, and the airspeed is 50h -1 Continuously heating to 700 ℃ for 60min, then heating to 900 ℃ for 60min, stopping introducing water vapor, and cooling to room temperature under vacuum condition, wherein the vacuum degree is-0.1 MPa.
Grinding the activated sample into powder according to the volume ratio of 1:3, mixing with a hydrochloric acid solution with the concentration of 20wt%, fully stirring for 8 hours, then carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under vacuum conditions to obtain the active carbon carrier.
(2) Catalyst preparation
4.3g of phosphoric acid H 3 PO 4 (concentration is 85. 85 wt%) is dissolved in 50mL of water, then 11.6g of molybdenum trioxide and 5.3g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the constant volume is 100mL after filtration, thus obtaining the Mo-Ni-P aqueous solution.
Adding the Mo-Ni-P water solution into 100g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h under vacuum, and roasting at 450 ℃ for 3h under nitrogen atmosphere to obtain the catalyst, wherein MoO 3 The content of NiO is 10.0wt%, the content of NiO is 2.5wt%, and P is 2 O 5 The content was 2.3wt%. The catalyst properties are listed in Table 1.
(3) Catalyst evaluation
The activity of the catalyst was evaluated by autoclave, and the properties of the raw oil used are shown in Table 2, and the evaluation conditions are: the reaction pressure is 15.0MPa, the reaction temperature is 430 ℃, the reaction time is 1h, the oil ratio is 13:1, and the evaluation results are shown in Table 3.
Example 2
(1) Carrier preparation
1000g of petroleum coke Jiao Yanmo to powder, then evenly mixing with 100g of calcium carbonate and 4000g of potassium carbonate, placing into a tube furnace, heating, introducing steam after the temperature exceeds 100 ℃, and controlling the airspeed to be 50h -1 Continuously heating to 700 ℃ for 60min, then heating to 900 ℃ for 60min, stopping introducing water vapor, and cooling to room temperature under vacuum condition, wherein the vacuum degree is-0.1 MPa.
Grinding the activated sample into powder according to the volume ratio of 1:3, mixing with a hydrochloric acid solution with the concentration of 20wt%, fully stirring for 8 hours, then carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under vacuum conditions to obtain the active carbon carrier.
(2) Catalyst preparation
6.5g of phosphoric acid H 3 PO 4 (concentration is 85. 85 wt%) is dissolved in 50mL of water, then 17.4g of molybdenum trioxide and 8.1g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the constant volume is 100mL after filtration, thus obtaining the Mo-Ni-P aqueous solution.
Adding the Mo-Ni-P water solution into 100g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 450 ℃ for 3h in nitrogen atmosphere to obtain the catalyst, wherein MoO 3 The content of NiO is 15.0wt%, the content of NiO is 3.8wt%, and P is 2 O 5 The content was 3.4wt%. The catalyst properties are listed in Table 1.
(3) Catalyst evaluation
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.
Example 3
(1) Carrier preparation
1000g of petroleum coke Jiao Yanmo to powder, then evenly mixing with 150g of calcium carbonate and 5000g of potassium carbonate, placing into a tube furnace, heating, introducing steam after the temperature exceeds 100 ℃, and controlling the airspeed to be 50h -1 Continuously heating to 700 ℃ for 60min, then heating to 900 ℃ for 60min, stopping introducing water vapor, and cooling to room temperature under vacuum condition, wherein the vacuum degree is-0.1 MPa.
Grinding the activated sample into powder according to the volume ratio of 1:3, mixing with a hydrochloric acid solution with the concentration of 20wt%, fully stirring for 8 hours, then carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under vacuum conditions to obtain the active carbon carrier.
(2) Catalyst preparation
8.6g of phosphoric acid H 3 PO 4 (concentration is 85. 85 wt%) is dissolved in 50mL of water, then 23.2g of molybdenum trioxide and 10.6g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the constant volume is 100mL after filtration, thus obtaining the Mo-Ni-P aqueous solution.
Mo-Ni-P aqueous solutionAll are added into 100g of prepared carrier, mixed evenly, stood for 3 hours, dried for 4 hours at 110 ℃, and baked for 3 hours at 450 ℃ under nitrogen atmosphere to obtain the catalyst, wherein MoO 3 The content of NiO is 20.0wt%, the content of NiO is 5.0wt%, and P is 2 O 5 The content was 4.6wt%. The catalyst properties are listed in Table 1.
(3) Catalyst evaluation
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.
Example 4
In example 3, phosphoric acid H 3 PO 4 12.9g (85. 85 wt%) of molybdenum trioxide 34.8g, basic nickel carbonate 15.9g and the same as in example 1 to obtain a catalyst wherein MoO 3 The content of NiO is 30.0wt%, the content of NiO is 7.5wt%, and P is 2 O 5 The content was 6.9wt%. The catalyst properties are listed in Table 1.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.
Example 5
In example 1, phosphoric acid H 3 PO 4 (concentration 85 wt%) was changed to 1.72g, molybdenum trioxide was changed to 4.64g, basic nickel carbonate was changed to 2.12g, and the same as in example 1 was used to obtain a catalyst in which MoO was contained 3 The content of NiO is 4.0wt%, the content of NiO is 1.0wt%, and P 2 O 5 The content was 0.92wt%. The catalyst properties are listed in Table 1.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.
Example 6
In example 1, 3000g of potassium carbonate was changed to 3000g of sodium carbonate, and the rest was the same as in example 1, to obtain a catalyst in which MoO 3 The content of NiO is 10.0wt%, the content of NiO is 2.5wt%, and P is 2 O 5 The content was 2.3wt%. The catalyst properties are listed in Table 1.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.
Example 7
In example 1, the water vapor treatment was performed at 700℃for 60min, then heated to 900℃for 60min, changed to 800℃for 120min, and the rest was the same as in example 1,obtaining a catalyst, wherein MoO 3 The content of NiO is 10.0wt%, the content of NiO is 2.5wt%, and P is 2 O 5 The content was 2.3wt%. The catalyst properties are listed in Table 1.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.
Example 8
In example 1, a catalyst was obtained in which MoO was obtained in the same manner as in example 1 except that 5.3g of basic nickel carbonate was changed to 5.2g of basic cobalt carbonate 3 10.0wt%, coO 2.5wt% and P 2 O 5 The content was 2.3wt%. The catalyst properties are listed in Table 1.
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.
Comparative example 1
(1) Carrier preparation
1000g of petroleum coke Jiao Yanmo to powder, 50g of calcium carbonate and 3000g of potassium carbonate are uniformly mixed, placed in a tube furnace, heated to 700 ℃ at constant for 60min, heated to 900 ℃ at constant for 60min, stopped introducing steam, cooled to room temperature under vacuum condition, and the vacuum degree is-0.1 MPa.
Grinding the activated sample into powder according to the volume ratio of 1:3, mixing with a hydrochloric acid solution with the concentration of 20wt%, fully stirring for 8 hours, then carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under vacuum conditions to obtain the active carbon carrier.
(2) Catalyst preparation
4.3g of phosphoric acid H 3 PO 4 (concentration is 85. 85 wt%) is dissolved in 50mL of water, then 11.6g of molybdenum trioxide and 5.3g of basic nickel carbonate are added, the temperature is raised to 100 ℃, the mixture is stirred and refluxed for 2.0h, and the constant volume is 100mL after filtration, thus obtaining the Mo-Ni-P aqueous solution.
Adding the Mo-Ni-P water solution into 100g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h under vacuum, and roasting at 450 ℃ for 3h under nitrogen atmosphere to obtain the catalyst, wherein MoO 3 The content of NiO is 10.0wt%, the content of NiO is 2.5wt%, and P is 2 O 5 The content was 2.3wt%. The catalyst properties are listed in Table 1.
(3) Catalyst evaluation
The catalyst was evaluated in the same manner as in example 1, and the evaluation results are shown in Table 3.
TABLE 1 physicochemical Properties of the catalysts
TABLE 2 oil Properties of raw materials
TABLE 3 evaluation results of catalysts
The results of the evaluation after the comparison with the activity of comparative example are shown in Table 3, with the activity of comparative example 1 being 100.
Claims (29)
1. A method for preparing a catalytic material with hydrogenation performance, the method comprising the following steps:
(1) Mixing petroleum coke, a pore-enlarging agent and an auxiliary agent, and contacting with water vapor for treatment after uniform mixing; the pore-expanding agent is one or more of calcium carbonate, calcium acetate, magnesium carbonate and magnesium acetate; the auxiliary agent is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium oxalate and sodium oxalate; the weight ratio of petroleum coke, pore-expanding agent and auxiliary agent is 1:0.02 to 0.20:1 to 7;
(2) Mixing the sample obtained in the step (1) with an acid solution, and further washing and drying to obtain a carrier;
(3) Preparing an aqueous solution containing a hydrogenation metal component and P from a compound containing the hydrogenation metal component, a phosphorus-containing compound and water;
(4) Mixing the aqueous solution obtained in the step (3) with the carrier obtained in the step (2), standing, drying and roasting to obtain the catalytic material.
2. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the pore-expanding agent in the step (1) is calcium carbonate.
3. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the auxiliary agent in the step (1) is potassium carbonate.
4. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: in the step (1), the weight ratio of petroleum coke, pore expanding agent and auxiliary agent is 1:0.05 to 0.15:2 to 6.
5. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the mass airspeed of the water vapor in the step (1) is 10 to 100 hours -1 。
6. The method for producing a catalytic material having hydrogenation properties according to claim 1 or 5, characterized in that: the mass airspeed of the water vapor in the step (1) is 20 to 80 hours -1 。
7. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the treatment process in the step (1) is as follows: the petroleum coke, the pore-enlarging agent and the auxiliary agent are uniformly mixed, and then the temperature is raised in the steam atmosphere, wherein the treatment temperature is 500-1000 ℃ and the treatment time is 30-240 min.
8. The method for producing a catalytic material having hydrogenation properties according to claim 1 or 7, characterized in that: the treatment process in the step (1) is as follows: the petroleum coke, the pore-enlarging agent and the auxiliary agent are uniformly mixed, and then the temperature is raised in the steam atmosphere, wherein the treatment temperature is 600-900 ℃, and the treatment time is 60-180 min.
9. The method for producing a catalytic material having hydrogenation properties according to claim 7, wherein: the treatment process comprises two sections, wherein the first section is treated for 15-120 min at 500-800 ℃, and then the temperature is raised to 800-1000 ℃ for the second section, and the time is 15-120 min.
10. The method for producing a catalytic material having hydrogenation properties according to claim 7, wherein: the treatment process comprises two sections, wherein the first section is treated for 15-120 min at 600-800 ℃, and then the temperature is raised to 800-1000 ℃ for the second section, and the time is 15-120 min.
11. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the acid solution in the step (2) is an inorganic acid solution, the inorganic acid solution is one or more of hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the acid solution is 10-30wt%.
12. The method for producing a catalytic material having hydrogenation properties according to claim 1 or 11, characterized in that: the acid solution in the step (2) is hydrochloric acid.
13. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: washing in the step (2) is water washing, firstly mixing the sample with deionized water, and carrying out solid-liquid separation after uniformly mixing until the pH value of the filtrate is neutral.
14. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the drying temperature in the step (2) is 100-200 ℃ and the drying time is 2-10 h.
15. A process for the preparation of a catalytic material having hydrogenation properties according to claim 1 or 14, characterized in that: the drying temperature in the step (2) is 120-180 ℃ and the drying time is 4-8 h.
16. A process for the preparation of a catalytic material having hydrogenation properties according to claim 1 or 14, characterized in that: the drying in step (2) is performed under vacuum.
17. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the compound containing the hydrogenation metal component in the step (3) is a compound containing VIB metal and/or a compound containing VIII metal, wherein the compound containing VIB metal is one or more of a molybdenum-containing compound and a tungsten-containing compound, and the compound containing VIII metal is one or more of a nickel-containing compound and a cobalt-containing compound.
18. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the phosphorus-containing compound in the step (3) is one or more of phosphoric acid, monoammonium phosphate and monoammonium phosphate.
19. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the concentration of the hydrogenation metal component in the aqueous solution containing the hydrogenation metal component and the P in the step (3) is 0.03-0.5 g/mL, and the concentration of the P is 0.002-0.05 g/mL.
20. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the drying temperature in the step (4) is 80-120 ℃ and the drying time is 4-12 h.
21. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: the roasting in the step (4) is carried out under an inert atmosphere, wherein the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton and xenon; the roasting temperature is 400-600 ℃, and the roasting time is 1-5 h.
22. The method for preparing a catalytic material having hydrogenation properties according to claim 1, wherein: introducing other metals into the carrier obtained in the step (2), wherein the other metals are one or more of Fe, zr, ti, B, la, ce.
23. A catalytic material having hydrogenation properties obtainable by the process of any one of claims 1 to 22.
24. The catalytic material having hydrogenation properties according to claim 23, wherein: the catalytic material with hydrogenation performance comprises a hydrogenation active metal component and a carrier, wherein the hydrogenation active metal component is one or more of VIB group metal and/or VIII group metal, and the carrier is petroleum coke-based active carbon.
25. The catalytic material having hydrogenation properties according to claim 23, wherein: the catalytic material with hydrogenation performance has the following properties: the specific surface area is 400-800 m 2 Per g, pore volume is 2.0-4.0 mL/g.
26. A process for hydrotreating a hydrocarbonaceous feedstock by mixing the hydrocarbonaceous feedstock with hydrogen into a reaction system, which is charged with catalytic material having hydrogenation properties as claimed in any one of claims 23 to 25.
27. The hydrocarbon-containing feed hydrotreating process as claimed in claim 26, wherein: the hydrocarbon-containing raw material is one or more of diesel oil, wax oil and residual oil.
28. The hydrocarbon-containing feed hydrotreating process as claimed in claim 26, wherein: the reaction conditions are as follows: the reaction temperature is 320-450 ℃, the reaction pressure is 6-18 MPa, the volume ratio of hydrogen to oil is 400-1000:1, and the volume airspeed is 0.1-3.0 h -1 。
29. The hydrocarbon-containing feed hydrotreating process as claimed in claim 26, wherein: the reaction conditions are as follows: the reaction temperature is 340-430 ℃, the reaction pressure is 8-15 MPa, the hydrogen-oil volume ratio is 500-800:1, and the volume airspeed is 0.2-2.0 h -1 。
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| CN104084222A (en) * | 2014-06-23 | 2014-10-08 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Residual oil hydrogenation catalyst and preparation method thereof |
| CN109912372A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | Synthesis gas methanation catalyst and its preparation method |
| CN109926076A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of liquefied coal coil hydrogenation catalyst and preparation method thereof |
| CN111097459A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104084222A (en) * | 2014-06-23 | 2014-10-08 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Residual oil hydrogenation catalyst and preparation method thereof |
| CN109912372A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | Synthesis gas methanation catalyst and its preparation method |
| CN109926076A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of liquefied coal coil hydrogenation catalyst and preparation method thereof |
| CN111097459A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
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