CN105833879B - A kind of hydrotreating catalyst and its preparation method and application - Google Patents
A kind of hydrotreating catalyst and its preparation method and application Download PDFInfo
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- CN105833879B CN105833879B CN201610286656.3A CN201610286656A CN105833879B CN 105833879 B CN105833879 B CN 105833879B CN 201610286656 A CN201610286656 A CN 201610286656A CN 105833879 B CN105833879 B CN 105833879B
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- alumina support
- metal
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- hydrotreating catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 142
- 229910052751 metal Inorganic materials 0.000 claims abstract description 80
- 239000002184 metal Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000008139 complexing agent Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 14
- 230000023556 desulfurization Effects 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 89
- 239000000243 solution Substances 0.000 claims description 70
- 239000000843 powder Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 32
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 24
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 24
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 24
- 239000001099 ammonium carbonate Substances 0.000 claims description 24
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 23
- 229940010552 ammonium molybdate Drugs 0.000 claims description 23
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 23
- 239000011609 ammonium molybdate Substances 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 229910001593 boehmite Inorganic materials 0.000 claims description 15
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 238000004898 kneading Methods 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 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 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 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 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- 238000007598 dipping method Methods 0.000 abstract description 21
- 230000004048 modification Effects 0.000 abstract description 21
- 238000012986 modification Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 20
- 239000002253 acid Substances 0.000 abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 230000003993 interaction Effects 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 239000005864 Sulphur Substances 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 54
- 239000008367 deionised water Substances 0.000 description 47
- 229910021641 deionized water Inorganic materials 0.000 description 47
- 235000015165 citric acid Nutrition 0.000 description 34
- 241000219793 Trifolium Species 0.000 description 22
- 241000219782 Sesbania Species 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 239000000908 ammonium hydroxide Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000004939 coking Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000005486 sulfidation Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006902 nitrogenation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910016556 Al2(MoO4)3 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 229910016550 Al2(WO4)3 Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- -1 aluminium form nickel aluminate Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000002119 pyrolysis Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J23/888—Tungsten
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of hydrotreating catalysts and its preparation method and application.The hydrotreating catalyst is using complexing agent roasting drying combination, alumina support is prepared first, then complexing agent surface dipping is carried out to it and modification by calcination handles to obtain modified aluminium oxide supports in inert gas, it finally uses isometric step impregnation carrying metal active component and directly drying exempts to roast, the hydrotreating catalyst is finally prepared.The preparation method of hydrotreating catalyst provided by the invention can be effectively improved the problem of alumina carrier surface L acid ratios are high, while can effectively weaken the strong interaction between active metal and alumina support；The hydrotreating catalyst being prepared is suitable for the high wax tailings hydrogenation desulfurization and denitrogenation process of sulphur, nitrogen content, not only with preferable hydrodenitrogenationactivity activity, but also has preferable hydrodesulfurization activity concurrently.
Description
Technical field
The invention belongs to catalyst fields, are related to a kind of hydrotreating catalyst and preparation method thereof and the hydrotreating is urged
Application of the agent in wax tailings hydrodenitrogeneration desulfurization.
Background technology
As world's crude oil heaviness, the aggravation of in poor quality trend and environmental regulation require not the quality on gasoline and diesel
Disconnected to improve, the delayed coking of inferior heavy oil, wax tailings are through hydrogenated processing as catalytic cracking or the raw material being hydrocracked.In order to
Light oil yield is improved to greatest extent, and fecund wax tailings inferior become the preferred technique of delayed coking.Thus, high nitrogen contains
The wax tailings hydrotreating inferior of amount proposes catalyst higher performance requirement.
The industrial catalyst of wax tailings hydrotreating at present is substantially using aluminium oxide as carrier, the main deficiency of such catalyst
There is alumina carrier surface there are higher L acid ratios, easily lead to the poisoning of coking gas oil hydrotreating catalyst nitrogen and coking deactivation；
Simultaneously because the strong interaction between aluminium oxide and active metal component, make that active metal curability is poor, hydrogenation activity is not high.
For this purpose, domestic and international researcher has been carried out centainly in carrier surface modification, raising catalyst metal components state of cure (vulcanization) etc.
Work.
CN1289828A discloses one kind with γ-Al2O3Or to contain SiO2γ-Al2O3Hydrofinishing for carrier is urged
Agent, catalyst is using W, Mo, Ni, P as active component.With SiO2Modified Al2O3Hydrogenation catalyst performance for carrier obtains one
It is fixed to improve, but its carrier acid amount is relatively low, and highly acid center is less, is unfavorable for the open loop fracture of azacyclo-, and denitrification activity is bad.
US4459367 discloses a kind of using HCl treatment aluminium oxide and the method for molecular sieve.This method by aluminium oxide with
Again with HCl treatment after molecular sieve mixed-forming, this processing mode can generate a certain number of macropores and mesoporous, but to oxidation
Aluminium is in itself there is also certain destruction and peptization, while to molecular sieve also there are stronger dealuminization, not only bad for carrier
Molding, and the acid of complex carrier is weakened, molecular sieve crystallinity declines, and is unfavorable for high hydrodenitrogenationactivity activity catalyst
Preparation.
CN101433848 discloses a kind of method that nonionic surfactant is added in active metal maceration extract, makes
The catalyst made from the method has the advantages that metal dispersion is good.But metal excessively dispersion is unfavorable for II types in sulfidation
The formation of metal active phase, it is not high to the absorption and hydrogenation and removing activity of the nitride of molecular structure complexity.
In conclusion regular oxidation alumina supporter interacts too strong between active metal, lead to active metal high degree of dispersion
It is unfavorable for the reduction and vulcanization of active metal, leads to that there are dispersion degrees using aluminium oxide as the load hydrogenation denitrification catalyst of carrier
High, the problem of curability is poor, alumina support is surface modified or adds organic additive in metal impregnation liquid merely
All there are the problem of active metal dispersion degree and undesirable sulphidity.Thus prepare with high hydrodenitrogenationactivity activity catalyst into
The critical issue in the urgent need to address for heavy oil hydrotreating field.
Invention content
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide a kind of preparation sides of hydrotreating catalyst
Method；This method can achieve the effect that high-efficiency desulfurization denitrogenation；
The present invention also aims to having of providing that the preparation method of above-mentioned hydrotreating catalyst is prepared it is high plus
The hydrotreating catalyst suitable for wax tailings of hydrogen activity；
The present invention also aims to provide above-mentioned hydrotreating catalyst answering in wax tailings hydrodenitrogeneration desulfurization
With.
The purpose of the present invention is achieved by the following technical programs：
A kind of preparation method of hydrotreating catalyst, includes the following steps：
Alumina powder, extrusion aid and expanding agent are mixed to get first material by step 1；Then binding agent is added to
Second material is mixed to get in first material；Second material is subjected to kneading, extrusion obtains wet stock, and the wet stock is carried out
Dry and calcination process, obtains alumina support；
Wherein, the quality of binding agent accounts for the 1wt%-5wt% of first material gross mass；The quality of expanding agent accounts for alumina powder
The 0.5wt%-15wt% of the quality at end；The quality of extrusion aid accounts for the 1wt%-15wt% of the quality of alumina powder；
Step 2 weighs complexing agent and is configured to enveloping agent solution, be impregnated in alumina carrier surface, then carries out
Dry and calcination process, obtains modified alumina support；
Wherein, the quality of complexing agent accounts for the 10wt%-25wt% of the quality of the alumina support；
Step 3 prepares the metal salt of active metal, and the metal salt for weighing the active metal of first part is configured to solution,
It is dipped into modified alumina support and is dried, obtain product A；Then complexing agent and second part are weighed
The metal salt of active metal be configured to mixed solution and be impregnated into product A, processing is then dried, obtains hydrotreating
Catalyst；
Wherein, in terms of reactive metal oxides, the content of the metal oxide of the active metal of first part is should add hydrogen
Handle the 10wt%-30wt% of the quality of catalyst；The content of the metal oxide of the active metal of second part is should add hydrogen
Handle the 1wt%-10wt% of the quality of catalyst；The metal oxide of the active metal of second part and the molar ratio of complexing agent
For 0.1-4.0:1.
In above-mentioned preparation method, it is preferable that the active metal can including Mo, W, Co and Ni etc. in it is one or more
Combination.
In above-mentioned preparation method, it is preferable that the metal salt of the active metal can include ammonium molybdate, ammonium metatungstate, nitre
One or more combinations in sour nickel and cobalt nitrate etc..
In the solution of the metal salt of the active metal, the metal salt containing Mo, W, Co, Ni is active constituent.Described
The metal salt of active metal of a part, the active metal of the second part metal salt be selected from the gold of the active metal
Belong to combination one or more in salt；The active metal of the metal salt of the active metal of the first part and the second part
Metal salt can be the same or different.Dissolved involved in above-mentioned preparation method the metal salt of active metal, complexing agent and match
Corresponding solution is made, the concentration no requirement (NR) for the solution of preparation, as long as guarantee is completely dissolved metal salt, the network of active metal
Mixture.
In above-mentioned preparation method, it is preferable that the alumina powder can include the fast shedding of aluminium oxide, aluminum oxide dry glue powder
With one or more combinations in boehmite powder etc.；The average pore size of the alumina powder is 6-14nm；
In above-mentioned preparation method, it is preferable that the specific surface area of the boehmite powder is 200-400m2, Kong Rongwei
0.6-1.3mL/g。
In above-mentioned preparation method, it is preferable that the extrusion aid can include one in sesbania powder, starch and polyvinyl alcohol etc.
Kind or a variety of combinations.
In above-mentioned preparation method, it is preferable that the complexing agent can include ethylenediamine tetra-acetic acid, ethylenediamine, citric acid and
One or more combinations in tartaric acid etc..
In above-mentioned preparation method, it is preferable that the binding agent is nitric acid, but not limited to this, the nitric acid mass percent
A concentration of 65%.
In above-mentioned preparation method, it is preferable that the expanding agent is ammonium hydrogen carbonate.
Above-mentioned binding agent and expanding agent according to specific embodiment, can be diluted with deionized water, be configured to not
Solution with concentration is used.
In above-mentioned preparation method, it is preferable that
In step 1, the temperature of drying process is 80-160 DEG C, time 2-8h；The temperature of calcination process is 400-
800 DEG C, time 1-5h；
In step 2, the temperature of drying process is 80-200 DEG C, time 2-8h；The process of calcination process is in argon gas
It is carried out in atmosphere, the temperature of calcination process is 200-800 DEG C, time 2-8h；
In step 3, the temperature of drying process is 80-200 DEG C, and the time is 2-8h.
The present invention also provides the hydrotreating catalysts that a kind of above-mentioned preparation method is prepared.The hydrorefining catalyst
Agent specific surface area is 200-400m2/ g, average pore size 6-13nm, Kong Rongwei 0.4-0.9mL/g；The hydrotreating catalyst has
There are high curing degree, appropriateness dispersion and high hydrogenation activity.
The present invention also provides a kind of application of above-mentioned hydrotreating catalyst in wax tailings hydrodenitrogeneration desulfurization, fit
For the high wax tailings hydrodenitrogeneration sweetening process of sulphur, nitrogen content.
Using complexing agent modified aluminas in the present invention, wax tailings hydrodenitrogenation catalyst performance can be improved.Oxidation
There are strong interaction between alumina supporter and metal, therefore metal Mo or W are easily and Al2O3Form Al2(MoO4)3Or Al2
(WO4)3Species, simultaneous oxidation aluminium form nickel aluminate with W metal, are unfavorable for jointly making between active metal in sulfidation
With formation hydrogenation metal activity phase.Using complexing agent dispersed active metal and before making it in sulfidation directly by active metal
It drives body and is converted into catalyst prepared by metal sulfide activated centre mode in sulfidation in the metal of carrier surface
Salt directly vulcanizes sulphidisation, can suitably prevent Al2(MoO4)3Or Al2(WO4)3The formation of species.To weaken between carrier and metal
Interaction promotes the type of the high hydrogenation metal activity phase of II types into the system of the wax tailings hydrodenitrogenation catalyst of the present invention
In Preparation Method, by impregnating complexing agent before alumina carrier surface and obtaining modified aluminium oxide after roasting in inert gas
Carrier is added organic complexing agent in maceration extract during supported active metals and is exempted from the method for roasting using directly drying.Gold-supported
Belong to active metal in rear catalyst in the form of metal salt in carrier surface to exist, metal salt is in sulfidation due to vulcanization temperature
Degree high metal salt is changed into sulphided state and carries out hydrogenation reaction, therefore the appropriate phase interaction prevented between metal oxide and carrier
With.On the one hand this combination preparation method between carrier surface modify strong phase effectively weakening active metal and alumina support
On the other hand interaction improves dispersion and the vulcanization of active metal so as to promote high add by the way of complexing agent carried metal
The coking gas oil hydrotreating catalyst with high hydrodenitrogenationactivity activity is prepared in the formation of hydrogen activity phase.
Beneficial effects of the present invention：
Preparation method the present invention provides hydrotreating catalyst can be effectively improved alumina carrier surface L acid ratios
The problem of high, while can effectively weaken the strong interaction between active metal and alumina support；The hydrotreating being prepared
Catalyst is suitable for the high wax tailings hydrogenation desulfurization and denitrogenation process of sulphur, nitrogen content, not only with preferable hydrodenitrogenationactivity activity, but also
Have preferable hydrodesulfurization activity concurrently.
Specific embodiment
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that the present invention can practical range restriction.
Aluminum hydroxide solid elastomer powder used in following embodiments is fast up to Chemical Group production, boehmite powder for Shandong
It is produced for Shandong Aluminum Plant, other reagents are commercially available chemical reagent.
Embodiment 1
A kind of preparation method of hydrotreating catalyst is present embodiments provided, is included the following steps：
Step 1：The aluminum oxide dry glue powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, 5.956g citric acids is then weighed and is dissolved in 63.5g's
Citric acid solution is prepared into deionized water solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is stood
12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C of temperature
The lower roasting 6h of degree, obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the ammonium molybdate of 31.526g
It is dissolved in the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, by the solution
It is impregnated into modified alumina support, room temperature stands 12h；By the alumina support of the modification after dipping in 120 DEG C of temperature
Lower dry 4h, obtains product A1；Then the citric acid of nickel nitrate and 17.326g for weighing 14.408g be dissolved in 63.5g go from
In sub- water, mixed solution is configured to, which is impregnated into product A1, after standing 12h under room temperature, is done at 120 DEG C
Dry 8h, obtains hydrotreating catalyst, is denoted as HDN-1.
Embodiment 2
A kind of preparation method of hydrotreating catalyst is present embodiments provided, is included the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, 5.956g citric acids is then weighed and is dissolved in 63.5g's
Citric acid solution is prepared into deionized water solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is stood
12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C of temperature
The lower roasting 6h of degree, obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the ammonium molybdate of 31.526g
It is dissolved in the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, by the solution
It is impregnated into modified alumina support, room temperature stands 12h；By the alumina support of the modification after dipping in 120 DEG C of temperature
Lower dry 4h, obtains product A2；Then the citric acid of nickel nitrate and 17.326g for weighing 14.408g be dissolved in 63.5g go from
In sub- water, mixed solution is configured to, which is impregnated into product A2, after standing 12h under room temperature, is done at 120 DEG C
Dry 8h, obtains hydrotreating catalyst, is denoted as HDN-2.
Embodiment 3
A kind of preparation method of hydrotreating catalyst is present embodiments provided, is included the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, 11.912g citric acids is then weighed and is dissolved in 63.5g's
Citric acid solution is prepared into deionized water solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is stood
12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C of temperature
The lower roasting 6h of degree, obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the ammonium molybdate of 31.526g
It is dissolved in the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, by the solution
It is impregnated into modified alumina support, room temperature stands 12h；By the alumina support of the modification after dipping in 120 DEG C of temperature
Lower dry 4h, obtains product A3；Then the citric acid of nickel nitrate and 17.326g for weighing 14.408g be dissolved in 63.5g go from
In sub- water, mixed solution is configured to, which is impregnated into product A3, after standing 12h under room temperature, is done at 120 DEG C
Dry 8h, obtains hydrotreating catalyst, is denoted as HDN-3.
Embodiment 4
A kind of preparation method of hydrotreating catalyst is present embodiments provided, is included the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, 5.956g citric acids is then weighed and is dissolved in 63.5g's
Citric acid solution is prepared into deionized water solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is stood
12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C of temperature
The lower roasting 6h of degree, obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the metatungstic acid of 20.342g
Ammonium is dissolved in the deionized water of 63.5g, stirs evenly and ammonium metatungstate solution is made, which is impregnated into modified aluminium oxide
In carrier, room temperature stands 12h；The alumina support of modification after dipping at a temperature of 120 DEG C is dried into 4h, obtains product
A4；Then the citric acid of nickel nitrate and 18.310g for weighing 15.266g is dissolved in the deionized water of 63.5g, is configured to mix
The mixed solution is impregnated into product A4 by solution, and after standing 12h under room temperature, dry 8h, obtains hydrotreating at 120 DEG C
Catalyst is denoted as HDN-4.
Embodiment 5
A kind of preparation method of hydrotreating catalyst is present embodiments provided, is included the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, 5.956g citric acids is then weighed and is dissolved in 63.5g's
Citric acid solution is prepared into deionized water solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is stood
12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C of temperature
The lower roasting 6h of degree, obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the ammonium molybdate of 31.526g
It is dissolved in the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, by the solution
It is impregnated into modified alumina support, room temperature stands 12h；By the alumina support of the modification after dipping in 120 DEG C of temperature
Lower dry 4h, obtains product A5；Then the tartaric acid of nickel nitrate and 16.657g for weighing 14.408g be dissolved in 63.5g go from
In sub- water, mixed solution is configured to, which is impregnated into product A5, after standing 12h under room temperature, is done at 120 DEG C
Dry 8h, obtains hydrotreating catalyst, is denoted as HDN-5.
Embodiment 6
A kind of preparation method of hydrotreating catalyst is present embodiments provided, is included the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, 5.956g citric acids is then weighed and is dissolved in 63.5g's
Citric acid solution is prepared into deionized water solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is stood
12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C of temperature
The lower roasting 6h of degree, obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the ammonium molybdate of 31.526g
It is dissolved in the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, by the solution
It is impregnated into modified alumina support, room temperature stands 12h；By the alumina support of the modification after dipping in 120 DEG C of temperature
Lower dry 4h, obtains product A6；Then the ethylenediamine tetra-acetic acid of nickel nitrate and 16.932g for weighing 14.408g is dissolved in 63.5g
Deionized water in, be configured to mixed solution, which be impregnated into product A6, under room temperature stand 12h after, in 120
Dry 8h, obtains hydrotreating catalyst, is denoted as HDN-6 at DEG C.
Embodiment 7
A kind of preparation method of hydrotreating catalyst is present embodiments provided, is included the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, the tartaric acid for then weighing 7.816g is dissolved in 63.5g
Deionized water solution in be prepared into citric acid solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is quiet
Put 12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C
Roasting temperature 6h obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the ammonium molybdate of 31.526g
It is dissolved in the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, by the solution
It is impregnated into modified alumina support, room temperature stands 12h；By the alumina support of the modification after dipping in 120 DEG C of temperature
Lower dry 4h, obtains product A7；Then the citric acid of nickel nitrate and 17.326g for weighing 14.408g be dissolved in 63.5g go from
In sub- water, mixed solution is configured to, which is impregnated into product A7, after standing 12h under room temperature, is done at 120 DEG C
Dry 8h, obtains hydrotreating catalyst, is denoted as HDN-7.
Embodiment 8
A kind of preparation method of hydrotreating catalyst is present embodiments provided, is included the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, 5.956g citric acids is then weighed and is dissolved in 63.5g's
Citric acid solution is prepared into deionized water solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is stood
12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C of temperature
The lower roasting 6h of degree, obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the ammonium molybdate of 31.526g
It is dissolved in the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, by the solution
It is impregnated into modified alumina support, room temperature stands 12h；By the alumina support of the modification after dipping in 120 DEG C of temperature
Lower dry 4h, obtains product A8；Then the citric acid of cobalt nitrate and 18.310g for weighing 15.278g be dissolved in 63.5g go from
In sub- water, mixed solution is configured to, which is impregnated into product A8, after standing 12h under room temperature, is done at 120 DEG C
Dry 8h, obtains hydrotreating catalyst, is denoted as HDN-8.
Comparative example 1
This comparative example provides a kind of preparation method of hydrotreating catalyst, includes the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned alumina supports being prepared of 50g are weighed, the ammonium molybdate for then weighing 31.526g is dissolved in
In the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, which is impregnated into
In alumina support, room temperature stands 12h；Alumina support after dipping is dried into 4h, 550 DEG C of temperature at a temperature of 120 DEG C
The lower roasting 3h of degree, obtains product B1；Then the nickel nitrate for weighing 14.408g is dissolved in the deionized water of 63.5g, is configured to nitre
The nickel nitrate solution is impregnated into product B1 by sour nickel solution, after standing 12h under room temperature, the dry 8h at 120 DEG C, 550 DEG C
Roasting temperature 3h, obtains hydrotreating catalyst, is denoted as Ref-1.
Comparative example 2
This comparative example provides a kind of preparation method of hydrotreating catalyst, includes the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned alumina supports being prepared of 50g are weighed, the ammonium molybdate for then weighing 31.526g is dissolved in
In the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, which is impregnated into
In alumina support, room temperature stands 12h；Alumina support after dipping is dried into 4h, 550 DEG C of temperature at a temperature of 120 DEG C
The lower roasting 3h of degree, obtains product B2；Then the citric acid of nickel nitrate and 17.326g for weighing 14.408g is dissolved in going for 63.5g
In ionized water, mixed solution is configured to, which is impregnated into product B2, after standing 12h under room temperature, at 120 DEG C
Dry 8h, 550 DEG C of roasting temperature 3h obtain hydrotreating catalyst, are denoted as Ref-2.
Comparative example 3
This comparative example provides a kind of preparation method of hydrotreating catalyst, includes the following steps：
Step 1：The boehmite powder of 200g, the sesbania powder of 8g are weighed, the ammonium bicarbonate soln for adding in 90mL is (every
The ammonium hydrogen carbonate of the deionized water addition 12g of 90mL is prepared) it is mixed evenly；Then it is (every that 90mL salpeter solutions are added
The nitric acid that the deionized water addition 10g mass percent concentrations of 90mL are 65% is prepared) it is mixed evenly to obtain material.In spiral shell
To material kneading 15min on swing arm banded extruder, the clover strip wet stock of a diameter of 1.5mm is made, then by clover item
Shape wet stock naturally dry for 24 hours after, dry 4h, is then transferred in Muffle furnace, at a temperature of 700 DEG C at a temperature of 120 DEG C
3h is roasted, obtains alumina support, the graininess which is broken into 20-40 mesh is spare.
Step 2：The above-mentioned broken alumina supports of 50g are weighed, 5.956g citric acids is then weighed and is dissolved in 63.5g's
Citric acid solution is prepared into deionized water solution, citric acid solution is then impregnated in alumina carrier surface, room temperature is stood
12h；Alumina support after dipping at a temperature of 120 DEG C is dried into 4h, is then placed in argon gas atmosphere, in 400 DEG C of temperature
The lower roasting 6h of degree, obtains modified alumina support.
Step 3：The alumina support of the above-mentioned modifications being prepared of 50g is weighed, then weighs the ammonium molybdate of 31.526g
It is dissolved in the deionized water of 63.5g, it is 9.5 to add in ammonium hydroxide and adjust pH value, stirs evenly and ammonium molybdate solution is made, by the solution
It is impregnated into modified alumina support, room temperature stands 12h；By the alumina support of the modification after dipping in 120 DEG C of temperature
Lower dry 4h, obtains product B3；Then the nickel nitrate for weighing 14.408g is dissolved in the deionized water of 63.5g, is configured to nitric acid
The nickel nitrate solution is impregnated into product B3 by nickel solution, and after standing 12h under room temperature, the dry 8h at 120 DEG C obtains adding hydrogen
Catalyst is handled, is denoted as Ref-3.
9 hydrotreating catalyst of embodiment is to the contrast experiment of the nitrogen and desulfurization performance of wax tailings
Hydrotreating catalyst prepared by the hydrotreating catalyst of embodiment 1-8 preparations and comparative example 1-3 is respectively adopted,
Nitrogen and desulfurization contrast experiment is carried out to wax tailings inferior.Sulfur content in the raw material poor quality wax tailings that use is tested as 3853
μ g/g, nitrogen content are 4465 μ g/g.
Evaluate the reaction condition of the hydrodenitrogeneration ability of hydrotreating catalyst：Temperature is 380 DEG C, pressure 8MPa, hydrogen
Oil volume ratio is 1000, volume space velocity 1h-1, the loadings of hydrotreating catalyst are 6mL；
Evaluate the reaction condition of the hydrodesulfurization ability of hydrotreating catalyst：Temperature is 320 DEG C, pressure 4MPa, sulphur
The change time be 6h, hydrogen-oil ratio 400, volume space velocity 1h-1。
The results are shown in Table 1 for evaluation experimental of the hydrotreating catalyst to the nitrogen and desulfurization performance of wax tailings：
Table 1
| Serial number | Raw material | Catalyst | HDN, % | HDS, % |
| 1 | Wax tailings | HDN-1 | 86.8 | 85.9 |
| 2 | Wax tailings | HDN-2 | 89.3 | 86.2 |
| 3 | Wax tailings | HDN-3 | 85.4 | 83.5 |
| 4 | Wax tailings | HDN-4 | 89.4 | 91.7 |
| 5 | Wax tailings | HDN-5 | 85.5 | 85.1 |
| 6 | Wax tailings | HDN-6 | 82.7 | 84.3 |
| 7 | Wax tailings | HDN-7 | 84.7 | 88.3 |
| 8 | Wax tailings | HDN-8 | 82.5 | 84.6 |
| 9 | Wax tailings | Ref-1 | 62.7 | 64.8 |
| 10 | Wax tailings | Ref-2 | 66.6 | 69.3 |
| 11 | Wax tailings | Ref-3 | 69.7 | 68.8 |
It is evaluated according to hydrodenitrogeneration reaction result, reality is determined using the method for the infrared adsorption-desorption of pyridine (Py-FTIR)
Apply the Acidity of the alumina support (being denoted as carrier 1) prepared in example 4 and modified alumina support (being denoted as carrier 2).It is adopted
It is MAGNA-IR560E.S.P type FTIR spectrum instrument with instrument, DTGS detectors, instrumental resolution 4cm-1。
The Surface L acid of the infrared spectrum representative sample recorded under the conditions of 200 DEG C and the total acid content of B acid, under the conditions of 350 DEG C
The middle strong acid amount of infrared spectrum representative sample Surface L acid and the B acid of record.Wherein 1540cm-1The B acid of sample is characterized at wave number
Amount, 1450cm-1The L acid amounts of sample are characterized at wave number.Experimental result is as shown in table 2.
Table 2
By table 1 the experimental results showed that：Hydrotreating prepared by the preparation method of hydrotreating catalyst provided by the invention
Catalyst has wax tailings preferable hydrodenitrogeneration desulfurization performance.The denitrification percent of wherein HDN-4 catalyst reaches 89.4%, takes off
Sulphur rate reaches 91.7%, is modified before individually being carried out using complexing agent to alumina support or is only used during Metal Supported
Catalyst Deitrogenatin rate prepared by complexing agent is up to 69.7%, and desulfurization degree is up to 69.3%.
According to 2 acid characterization data of table：The strong L acid ratio of the alumina support of one side complexing agent modification subtracts
Few, weak L acid increasing proportion, total acid content is declined, therefore can suitably weaken carrier and activity in active metal loading process
Intermetallic interaction；Collaboration prepares catalyst using complexing agent and the mode for exempting to roast during Metal Supported simultaneously,
The sintering of active metal is effectively hindered, therefore the catalyst series all have higher desulfurization and denitrification percent.
In conclusion the preparation method of hydrotreating catalyst provided by the invention can be effectively improved carrying alumina body surface
The problem of face L acid ratios are high, while can effectively weaken the strong interaction between active metal and alumina support；It is prepared
Hydrotreating catalyst is suitable for the high wax tailings hydrogenation desulfurization and denitrogenation process of sulphur, nitrogen content, has both had preferably plus hydrogen takes off
Nitrogen activity, and have preferable hydrodesulfurization activity concurrently.
Claims (13)
1. a kind of preparation method of hydrotreating catalyst, includes the following steps：
Alumina powder, extrusion aid and expanding agent are mixed to get first material by step 1；Then binding agent is added to first
Second material is mixed to get in material；Second material is subjected to kneading, extrusion obtains wet stock, and the wet stock is dried
And calcination process, obtain alumina support；
Wherein, the quality of binding agent accounts for the 1wt%-5wt% of first material gross mass；The quality of expanding agent accounts for alumina powder
The 0.5wt%-15wt% of quality；The quality of extrusion aid accounts for the 1wt%-15wt% of the quality of alumina powder；
Step 2 weighs complexing agent and is configured to enveloping agent solution, is impregnated in alumina carrier surface, is then dried
And calcination process, obtain modified alumina support；
Wherein, the quality of complexing agent accounts for the 10wt%-25wt% of the quality of the alumina support；
Step 3 prepares the metal salt of active metal, and the metal salt for weighing the active metal of first part is configured to solution, by it
It is impregnated into modified alumina support and is dried, obtain product A；Then the work of complexing agent and second part is weighed
The metal salt of property metal is configured to mixed solution and is impregnated into product A, and processing is then dried, obtains hydrorefining catalyst
Agent；
Wherein, in terms of reactive metal oxides, the content of the metal oxide of the active metal of first part is the hydrotreating
The 10wt%-30wt% of the quality of catalyst；The content of the metal oxide of the active metal of second part is the hydrotreating
The 1wt%-10wt% of the quality of catalyst；The metal oxide of the active metal of second part and the molar ratio of complexing agent are
0.1-4.0:1。
2. preparation method according to claim 1, it is characterised in that：The active metal is included in Mo, W, Co and Ni
One or more combinations.
3. preparation method according to claim 1, it is characterised in that：The metal salt of the active metal include ammonium molybdate,
One or more combinations in ammonium metatungstate, nickel nitrate and cobalt nitrate.
4. preparation method according to claim 2, it is characterised in that：The metal salt of the active metal include ammonium molybdate,
One or more combinations in ammonium metatungstate, nickel nitrate and cobalt nitrate.
5. preparation method according to claim 1, it is characterised in that：The alumina powder include the fast shedding of aluminium oxide,
One or more combinations in aluminum oxide dry glue powder and boehmite powder；The average pore size of the alumina powder is 6-
14nm。
6. preparation method according to claim 5, it is characterised in that：The specific surface area of the boehmite powder is
200-400m2, Kong Rongwei 0.6-1.3mL/g.
7. preparation method according to claim 1, it is characterised in that：The extrusion aid includes sesbania powder, starch and poly- second
One or more combinations in enol.
8. preparation method according to claim 1, it is characterised in that：The complexing agent includes ethylenediamine tetra-acetic acid, second two
One or more combinations in amine, citric acid and tartaric acid.
9. preparation method according to claim 1, it is characterised in that：
The binding agent is nitric acid, and the nitric acid mass percent concentration is 65%.
10. preparation method according to claim 9, it is characterised in that：The expanding agent is ammonium hydrogen carbonate.
11. preparation method according to claim 1, it is characterised in that：
In step 1, the temperature of drying process is 80-160 DEG C, time 2-8h；The temperature of calcination process is 400-800 DEG C,
Time is 1-5h；
In step 2, the temperature of drying process is 80-200 DEG C, time 2-8h；The process of calcination process is in argon gas atmosphere
Middle progress, the temperature of calcination process is 200-800 DEG C, time 2-8h；
In step 3, the temperature of drying process is 80-200 DEG C, and the time is 2-8h.
12. the hydrotreating that the preparation method of the hydrotreating catalyst described in claim 1-11 any one is prepared is urged
Agent, it is characterised in that：The specific surface area of the hydrotreating catalyst is 200-400m2/ g, average pore size 6-13nm, Kong Rong
For 0.4-0.9mL/g.
13. application of the hydrotreating catalyst in wax tailings hydrodenitrogeneration desulfurization described in claim 12.
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| CN103212432A (en) * | 2013-04-01 | 2013-07-24 | 中国石油天然气集团公司 | Catalyst for hydro-denitrification of inferior heavy distillate oil and preparation method and application of catalyst |
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| CN103212432A (en) * | 2013-04-01 | 2013-07-24 | 中国石油天然气集团公司 | Catalyst for hydro-denitrification of inferior heavy distillate oil and preparation method and application of catalyst |
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