CN115672347A - Hydrofining catalyst and preparation method and application thereof - Google Patents
Hydrofining catalyst and preparation method and application thereof Download PDFInfo
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- CN115672347A CN115672347A CN202110864141.8A CN202110864141A CN115672347A CN 115672347 A CN115672347 A CN 115672347A CN 202110864141 A CN202110864141 A CN 202110864141A CN 115672347 A CN115672347 A CN 115672347A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 55
- 150000001993 dienes Chemical class 0.000 claims abstract description 46
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 41
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 14
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 26
- 238000012986 modification Methods 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 22
- 238000011068 loading method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- 150000005673 monoalkenes Chemical class 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 20
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 16
- 239000004480 active ingredient Substances 0.000 description 14
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 13
- 150000001345 alkine derivatives Chemical class 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 3
- 239000004439 Isononyl alcohol Substances 0.000 description 3
- 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 3
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- -1 lanthanum magnesium aluminate Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002156 mixing Methods 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Abstract
The invention provides a hydrofining catalyst and a preparation method and application thereof. The hydrofining catalyst comprises Al 2 O 3 ‑TiO 2 Composite oxide and Al supported on the same 2 O 3 ‑TiO 2 The modified component comprises cobalt and/or cobalt oxide and cerium and/or cerium oxide, and the active component comprises molybdenum and/or molybdenum oxide and nickel and/or nickel oxide. The hydrofining catalyst provided by the invention has higher hydrogenation activity, can start hydrogenation reaction at lower inlet temperature, and especially can start hydrogenation reaction at C with low diolefin content 4 The saturated hydrogenation reaction of the fraction greatly reduces the energy consumption.
Description
Technical Field
The invention relates to C with low diolefin content 4 The technical field of fraction hydrogenation, in particular to a hydrofining catalyst and a preparation method and application thereof.
Background
The prior art focuses on hydrotreating carbon four-fraction with high contents of diolefin and alkyne, but petrochemical enterprises often have a low diolefin carbon four-fraction raw material, such as ether-carbon four or isononyl alcohol carbon four, which has low recycling value, and the raw material directly fed into an ethylene cracking furnace is urgently needed to be subjected to hydrogenation saturation because the olefin content is high and the stability of the cracking furnace is affected.
CN 109468141A discloses a C 4 A saturated hydrogenation method of distillate, which adopts a fixed bed reactor; the catalyst is a nickel hydrogenation catalyst, and comprises main active components of molybdenum, nickel, cobalt, potassium and silicon oxide-aluminum oxide compositions, wherein the main active components comprise, by weight, 26-36wt% of nickel oxide, 0.05-2.5wt% of molybdenum oxide, 0.1-2.5 wt% of cobalt oxide, 2.5-7.5wt% of potassium oxide and 0-2.2wt% of one or two auxiliary agents selected from oxides of strontium and manganese; the content of the silicon oxide-aluminum oxide composition is 35-70wt%, and the silicon oxide-aluminum oxide composition comprises 0.1-16 wt% of silicon oxide, 0.5-15 wt% of nickel-containing lanthanum magnesium aluminate and 60-86.0 wt% of aluminum oxide; the hydrogenation process conditions are as follows: the inlet temperature of the reactor is 30-60 ℃, the reaction pressure is 1.5-6.0 MPa, and the liquid volume space velocity is 1.0-6.0 h -1 The volume ratio of hydrogen to oil is 100-400.
Although the above process enables the inlet temperature of the reactor to be reduced, it processes feedstocks having a high total content of diolefins and acetylenes, in the example 19wt%, which is not specific to the low diolefin carbon four cut, and the catalyst suffers from the following disadvantages: firstly, the poisoning resistance is poor due to the fear of sulfur, chlorine, water, acetonitrile, DMF and other impurities; secondly, the stability is poor.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a hydrofining catalyst, which has high hydrogenation activity and can start hydrogenation reaction at low inlet temperature by using specific carrier, modifying component and active component, especially C with low diolefin content 4 The saturated hydrogenation reaction of the fraction greatly reduces the energy consumption.
The second purpose of the present invention is to provide a process for producing a hydrorefining catalyst corresponding to the first purpose.
The third object of the present invention is to provide a use of a hydrorefining catalyst corresponding to the above object.
The fourth object of the present invention is to provide C having a low diolefin content which corresponds to the above object 4 A method for hydrogenating distillate.
In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:
a hydrorefining catalyst comprising Al 2 O 3 -TiO 2 Composite oxide and Al supported on the same 2 O 3 -TiO 2 The modified component comprises cobalt and/or cobalt oxide and cerium and/or cerium oxide, and the active component comprises molybdenum and/or molybdenum oxide and nickel and/or nickel oxide.
In some preferred embodiments of the present invention, the Al is 2 O 3 -TiO 2 The total mass of the composite oxide is calculated as the reference, al 2 O 3 The content of (A) is 70wt% -90 wt%; tiO 2 2 The content of (A) is 10wt% -30 wt%.
According to the invention, the Al 2 O 3 -TiO 2 The shape of the composite oxide is selected from granular, spherical, gear-shaped, leaf-shaped, strip-shaped or tri-shapedOne or more of a clover-like shape, preferably a clover-like shape.
According to the invention, the Al 2 O 3 -TiO 2 The composite oxide can be obtained from a commercially available source or can be prepared by a self-made method. Illustratively, the Al 2 O 3 -TiO 2 The preparation method of the composite oxide comprises the following steps:
a) Mixing an aluminum-containing solution, a titanium-containing solution and an alkaline solution, and performing coprecipitation to obtain a precipitate;
b) Drying and roasting the precipitate to obtain the Al 2 O 3 -TiO 2 A composite oxide.
According to the invention, in step a), the flow rate of the alkaline solution is controlled so that the precipitate is kept in the range of 5.0 to 6.0 for 5 to 10 minutes, preferably 8 minutes, the flow rate of the alkaline solution is increased again so that the pH value of the mixed solution is kept in the range of 8.5 to 9.5 for 5 to 10 minutes, preferably 8 minutes, then the flow rate of the alkaline solution is decreased so that the pH value of the mixed solution is kept in the range of 5.0 to 6.0 for 5 to 10 minutes, preferably 8 minutes, the flow rate of the alkaline solution is increased again so that the pH value of the precipitate is kept in the range of 8.5 to 9.5, and the process is repeated until all the aluminum-containing solution and the titanium-containing solution are added.
According to the invention, in step a), the solution containing aluminium can be a solution prepared by dissolving a soluble salt of aluminium in water; the titanium-containing solution may be a solution prepared by dissolving a soluble salt of titanium in benzene. The soluble salt of aluminum can be aluminum sulfate, aluminum nitrate or aluminum chloride, and the soluble salt of titanium can be Ti (OCH) 2 CH 3 )。
According to the invention, in step b), the alkaline solution may be NH 4 HCO 3 And a mixed solution of ammonia water and water. Wherein the ammonia water is concentrated ammonia water with the concentration of 25wt% -28 wt%. In one embodiment, 10-30g of NH 4 HCO 3 Dissolving (analytically pure) into 600mL of deionized water, then adding 200 mL-300 mL of ammonia water with the concentration of 25wt% -28 wt%, uniformly stirring, and then adding a certain volume of deionized water to prepare 1000mL of alkaline solution.
According to the invention, in step b), the drying conditions may be: the temperature is 90-150 ℃, and the time is 1-24 h; the conditions of calcination may be: the temperature is 350-550 ℃, and the time is 1-24 h.
According to the present invention, the precipitate may be filtered and washed before being dried. Filtration and washing are conventional operations in the art and are not described in detail herein.
In some other embodiments of the present invention, the Al 2 O 3 -TiO 2 The composite oxide is preferably a titanium oxide-alumina composite carrier provided in patent CN 104971706B.
In some preferred embodiments of the present invention, the hydrofinishing catalyst is prepared by first subjecting the Al to hydrogenation treatment 2 O 3 -TiO 2 The composite oxide is prepared by loading the modified component and then loading the active component.
In some preferred embodiments of the present invention, the active component is loaded with molybdenum and then nickel.
In some preferred embodiments of the present invention, the cobalt and/or cobalt oxide content is from 0.5wt% to 2wt%, based on the total mass of the hydrofinishing catalyst; the content of cerium and/or cerium oxide is 1-3 wt%; the content of molybdenum and/or molybdenum oxide is 8wt% -20 wt%; the content of nickel and/or nickel oxide is 4wt% -12 wt%.
In some preferred embodiments of the present invention, the hydrofinishing catalyst has a specific surface area of 150m 2 /g～400m 2 (ii)/g; the pore volume is 0.3 mL/g-0.8 mL/g.
In some preferred embodiments of the present invention, the hydrofinishing catalyst has a specific surface area of 150m 2 /g～300m 2 (ii)/g; the pore volume is 0.3 mL/g-0.6 mL/g.
In some preferred embodiments of the invention, the modifying component further comprises calcium and/or an oxide of calcium. The content of calcium and/or calcium oxide is 0.1wt% -1 wt% based on the total mass of the hydrofining catalyst.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a method for preparing a hydrofinishing catalyst according to any one of the preceding embodiments, comprising:
s1, adopting impregnating solution containing cobalt element and cerium element to treat Al 2 O 3 -TiO 2 Impregnating the composite oxide, drying and roasting a product obtained after impregnation to obtain the surface modified Al 2 O 3 -TiO 2 A composite oxide;
s2, adopting impregnation liquid containing molybdenum element to carry out surface modification on the Al 2 O 3 -TiO 2 Impregnating the composite oxide, and drying and roasting a product obtained after impregnation to obtain a catalyst precursor;
and S3, impregnating the catalyst precursor by using an impregnating solution containing a nickel element, and drying and roasting a product obtained after impregnation to obtain the hydrofining catalyst.
In some preferred embodiments of the present invention, the impregnation solution containing cobalt and cerium further contains calcium.
In some preferred embodiments of the present invention, in step S1, the conditions of the roasting treatment include a temperature of 450 to 650 ℃, preferably 500 to 600 ℃; the time is 1h to 24h, preferably 2h to 12h.
In some preferred embodiments of the present invention, in step S2, the conditions of the roasting treatment include a temperature of 450 to 650 ℃, preferably 500 to 600 ℃; the time is 1h to 24h, preferably 2h to 12h.
In some preferred embodiments of the present invention, in step S3, the conditions of the roasting treatment include a temperature of 450 to 650 ℃, preferably 500 to 600 ℃; the time is 1h to 24h, preferably 2h to 12h.
According to the present invention, in the above-mentioned production method, the respective substances are used in such an amount that the content of each component of the produced hydrorefining catalyst is within the range defined in any one of the above-mentioned embodiments.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
use of a hydrofinishing catalyst according to any one of the preceding embodiments or of a hydrofinishing catalyst prepared by a process according to any one of the preceding embodiments in the field of catalysts for saturated hydrogenation, preferably in the field of catalysts for saturated hydrogenation of a fraction having a low diolefin content, wherein the diolefin content of the fraction having a low diolefin content is not higher than 2wt%, preferably not higher than 1wt%.
According to the invention, the hydrofining catalyst is used for one-step saturated hydrogenation. The one-step saturated hydrofining catalyst in the prior art is usually used for materials with diolefin content not higher than 1wt%, because the hydrogenation reaction is unstable due to the high diolefin content. The hydrofining catalyst provided by the invention has good low-temperature activity, low inlet temperature and less coking of diolefin, so that the hydrofining catalyst can be used for materials with the diolefin content higher than 1wt% and not higher than 2wt%.
According to the present invention, before the hydrorefining catalyst provided by the present invention is used in hydrogenation reaction, it may be subjected to a sulfiding treatment. The vulcanization treatment is a conventional pretreatment means in the art, and the present invention is not intended to be unduly limited thereto. Illustratively, the curing process includes: under the hydrogen pressure of 2.0-3.5MPa, the hydrogen-oil ratio of 300-500 and the temperature of 300-350 ℃, for 2-5h -1 The stream volume space velocity of (A) is introduced into 10 to 30h of a dimethyldisulfide (DMDS) -containing sulfurized oil.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
c with low content of diolefin 4 A process for hydrogenating a distillate comprising: c with low diolefin content 4 Contacting the fraction with the hydrofining catalyst according to any one of the above embodiments or the hydrofining catalyst prepared by the preparation method according to any one of the above embodiments, thereby treating the C with low diolefin content 4 And (3) carrying out hydrogenation treatment on the fraction to obtain a hydrogenated product, wherein the content of the diolefin in the fraction with the low content of the diolefin is not higher than 2wt%, and preferably not higher than 1wt%.
In some preferred embodiments of the invention, the fraction with a low diolefin content contains from 5wt% to 50wt% of monoolefins.
In some preferred embodiments of the invention, the contacting occurs in a reactor and the operating conditions of the reactor include: the pressure is 2.0MPa to 3.5MPa; the inlet temperature is 40-80 ℃; the volume space velocity is 0.3h -1 ～2.0h -1 (ii) a The volume ratio of the hydrogen to the fresh raw material is 30-300.
In some preferred embodiments of the invention, a portion of the hydrogenation product is recycled in a recycle ratio of from 5 to 15.
According to the present invention, the outlet temperature is determined by conditions such as the inlet temperature and the circulation ratio, and therefore the present invention is not limited to the outlet temperature. In some embodiments, when the inlet temperature and the recycle ratio are within the above ranges, the outlet temperature is from 90 ℃ to 120 ℃.
According to the invention, C has a low diolefin content 4 The fraction can be C four after ether and C four after isononyl alcohol extraction.
In the present invention, the term "fresh feedstock" means newly added C having a low diolefin content 4 And (6) cutting.
In the present invention, the term "recycle ratio" refers to the volume ratio of hydrogenation product to fresh feed for recycle. For example, 50mL of fresh C is fed 4 While recycling 200mL of the hydrogenation product, the recycle ratio is 4:1.
the invention has the beneficial effects that: the hydrofining catalyst provided by the invention can start hydrogenation reaction at a lower starting temperature, and can realize that C with low diolefin content can be obtained by only adopting one reactor 4 The distillate is hydrogenated to a mono-olefin content of less than 0.5 wt.%. The catalyst has good impurity resistance, has high resistance to impurities such as sulfur, chlorine, acetonitrile, DMF (dimethyl formamide), free water and the like in the raw materials, can effectively avoid catalyst poisoning caused by unstable control of the impurities in the raw materials, and has good operation stability.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available from commercial sources.
In the following embodiments, unless otherwise specified, the composition analysis of the hydrogenated material was performed while the apparatus was operating for 96 hours.
In the following embodiments, unless otherwise specified, the content of each substance in the hydrogenated product is detected by a gas chromatography method.
In the following embodiments, unless otherwise specified, the content of active components in the catalyst is determined by X-ray fluorescence test (XRF) analysis.
Example 1
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
178.5g of AlCl 3 ·6H 2 Placing O (analytically pure) in 1000mL of deionized water to prepare a solution A1; 430.7g of Ti (OCH) 2 CH 3 ) 4 (chemical purity) was dissolved in 500mL of benzene (benzene content 99.8 wt%) to prepare a solution B1; 18g of NH 4 HCO 3 (analytically pure) is dissolved in 600mL of deionized water, then 250mL of ammonia water with the concentration of 26wt% is added, the mixture is stirred uniformly, and then deionized water with a certain volume is added to prepare 1000mL of solution C1.
Under the conditions of normal pressure and 73 ℃, three solutions of A1, B1 and C1 are subjected to co-current coprecipitation. Controlling the flow rate of the solution C1 to keep the pH value of the precipitate within the range of 5.0-6.0 for 8 minutes, increasing the flow rate of the solution C1 to keep the pH value of the mixed solution within the range of 8.5-9.5 for 8 minutes, then reducing the flow rate of the solution C1 to keep the pH value of the mixed solution within the range of 5.0-6.0 for 8 minutes, increasing the flow rate of the solution C1 to keep the pH value of the precipitate within the range of 8.5-9.5, and repeating the steps until the solution A1 and the solution B1 are completely added to prepare the reaction solution.
The obtained reaction solution was allowed to stand at 70 ℃ for 30 minutesFiltering after a while to prepare a filter cake. Then washing the filter cake with deionized water 15 times the volume of the filter cake for 30 minutes, filtering, washing again, repeating the process four times, finally drying the filter cake at 110 ℃ for 10 hours, and roasting at 450 ℃ for 5 hours to obtain 42.7g of Al 2 O 3 -TiO 2 A composite oxide support (designated as Z1). Wherein, tiO 2 15.14%, the balance being Al 2 O 3 。
b) Modification of the surface of a support
Preparing a mixed solution of cobalt nitrate and cerium nitrate by using a volumetric flask, impregnating 100g of the carrier Z1 prepared in the step a) for 2 hours at normal temperature, drying for 4 hours at 110 ℃ after filtering, and roasting for 4 hours at 550 ℃ to complete the modification of the carrier Z1, wherein the modified carrier is marked as Z2. The cobalt oxide content in the Z2 carrier was 1.2wt%, and the cerium oxide content was 1.5wt%.
c) Loading of active ingredients
Preparing 26.68g/100mL ammonium molybdate tetrahydrate by using a volumetric flask and 14wt% ammonia water, impregnating 100g of the carrier Z2 prepared in the step b) at normal temperature for 2 hours, filtering, drying at 110 ℃ overnight, and roasting at 550 ℃ for 4 hours to complete the loading of the molybdenum oxide serving as an active component, thereby preparing a catalyst precursor Z3.
Then putting the catalyst precursor Z3 loaded with molybdenum oxide into 39.48g/100mL nickel nitrate hexahydrate, soaking at normal temperature for 2h, filtering, drying at 110 ℃ overnight, and roasting at 550 ℃ for 4h to obtain MoO 3 MoO with a content of 14.1wt% and NiO with a content of 7.5wt% 3 -CoO/Al 2 O 3 -TiO 2 The catalyst A of (1).
The specific surface area of the catalyst A is 286m 2 (iv) g; the pore volume was 0.39mL/g.
B. Hydrogenation reaction
A certain isononyl alcohol device is adopted to extract carbon four raw material A, and the raw material composition is as follows:
butene-1: 0.44wt%; and (3) trans-butene: 10.31wt%; isobutene: 4.03wt%; isobutane: 11.43wt%; n-butane: 72.46wt%; maleic acid: 0.32wt%; butadiene: <2 wt.%.
Finishing to obtain: and (3) diolefin: <1wt%; mono-olefins: 15.1wt%; the balance being alkanes.
A 100mL scale fixed bed reactor is filled with 100mL of hydrogenation catalyst A to carry out a sulfurization reaction, and the sulfurization conditions are as follows: hydrogen pressure 2.0MPa, hydrogen-oil ratio 300-500, and temperature 300 ℃, for 2h -1 The stream volume space velocity of (2) was passed over 15h of a sulphurised oil containing 3wt% dimethyldisulphide (DMDS).
The hydrogenation reaction is carried out after the sulfurization reaction, and the operation conditions of the hydrogenation reactor are as follows: the pressure is 2.8MPa, the inlet temperature is 50 ℃, and the volume space velocity is 2.0h -1 The volume ratio of hydrogen to fresh raw material is 160; the circulation ratio is 3.
Reactor outlet product composition: no alkyne and diene, the content of monoolefine is 0.82wt%.
Example 2
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
TiO preparation Using the method of example 1 with adjustment of the amount of titanium salt added 2 25wt% of Al in balance 2 O 3 The composite oxide support (designated as Z1) of (2).
b) Modification of the surface of a support
The modified support having a cobalt oxide content of 0.83wt% and a cerium oxide content of 1.90wt%, denoted as Z2, was prepared using the method of example 1 with the addition amounts of cobalt nitrate and cerium nitrate adjusted.
c) Loading of active ingredients
MoO was prepared using the method of example 1, with the addition of ammonium molybdate tetrahydrate and nickel nitrate hexahydrate adjusted 3 MoO with content of 12wt% and NiO content of 11wt% 3 -CoO/Al 2 O 3 -TiO 2 The catalyst B of (1).
The specific surface area of the catalyst B is 272m 2 (ii)/g; the pore volume was 0.37mL/g.
B. Hydrogenation reaction
The ether-carbon four raw material is used and comprises the following components:
butene-1: 0.22wt%; and (3) trans-butene: 35.62wt%; isobutene: <0.01wt%; isobutane: 16.35wt%; n-butane: 35.87wt%; maleic acid: 11.08wt%; butadiene <0.1wt%.
Finishing to obtain: diolefin <0.1wt%; mono-olefins: 46.92wt%; the balance being alkanes.
And (2) filling 100mL of hydrogenation catalyst B into a 100 mL-scale fixed bed reactor, and carrying out a vulcanization reaction under the vulcanization conditions: hydrogen pressure 2.0MPa, hydrogen-oil ratio 300-500, and temperature 300 ℃, for 2h -1 The stream volume space velocity of (2) was passed over 18h of a sulphurised oil containing 2wt% dimethyldisulphide (DMDS).
The sulfurization reaction is followed by a hydrogenation reaction, and the operating conditions of the hydrogenation reactor are as follows: the pressure is 3.5MPa, the inlet temperature is 40 ℃, and the volume space velocity is 0.5h -1 The volume ratio of hydrogen to fresh raw material is 160; the circulation ratio is 12.
Reactor outlet product composition: no alkyne and diene, and the content of monoolefine is 0.3wt%.
Example 3
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
The composite oxide support (designated as Z1) of example 1 was used.
b) Modification of the surface of a support
By adjusting the amounts of cobalt nitrate and cerium nitrate added, a modified support having a cobalt oxide content of 0.58wt% and a cerium oxide content of 0.76wt%, denoted as Z2, was prepared using the method of example 1.
c) Loading of active ingredients
MoO was prepared using the method of example 1, with the addition of ammonium molybdate tetrahydrate and nickel nitrate hexahydrate adjusted 3 MoO with 11wt% of NiO and 9.5wt% of NiO 3 -CoO/Al 2 O 3 -TiO 2 Catalyst C of (1).
The specific surface area of the catalyst C is 276m 2 (iv) g; the pore volume was 0.37mL/g.
B. Hydrogenation reaction
The hydrogenation feed of example 1 was used.
And (2) filling 100mL of hydrogenation catalyst C in a 100 mL-scale fixed bed reactor, and carrying out a vulcanization reaction under the vulcanization conditions: hydrogen pressure 2.0MPa, hydrogen-oil ratio 300-500, and temperature 300 ℃, for 2h -1 The stream volume space velocity of (2) was passed over 15h of a sulphurised oil containing 3wt% dimethyldisulphide (DMDS).
The hydrogenation reaction is carried out after the sulfurization reaction, and the operation conditions of the hydrogenation reactor are as follows: the pressure is 2.5MPa, the inlet temperature is 60 ℃, and the volume space velocity is 1.5h -1 The volume ratio of the hydrogen to the fresh raw material is 200; the circulation ratio is 5.
Reactor outlet product composition: no alkyne and diene, and the content of monoolefine is 0.12wt%.
Example 4
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
The composite oxide support (designated as Z1) of example 1 was used.
b) Modification of the surface of a support
Preparing a cobalt nitrate solution by using a volumetric flask, impregnating 100g of the carrier Z1 prepared in the step a) for 2 hours at normal temperature, drying for 4 hours at 110 ℃ after filtering, and roasting for 4 hours at 550 ℃ to finish the primary modification of the carrier Z1, wherein the carrier after the primary modification is recorded as Z2.
Preparing a cerium nitrate solution by using a volumetric flask, impregnating 100g of the carrier Z2 prepared in the step a) for 2 hours at normal temperature, drying at 110 ℃ for 4 hours after filtering, and roasting at 550 ℃ for 4 hours to complete the modification of the carrier Z2, wherein the modified carrier is marked as Z3.
The cobalt oxide content in the Z3 carrier was 1.5wt%, and the cerium oxide content was 1.23wt%.
c) Loading of active ingredients
The same procedure as in example 1. To obtain MoO 3 MoO with a content of 14.1wt% and NiO with a content of 7.5wt% 3 -CoO/Al 2 O 3 -TiO 2 Catalyst D according to (1).
The specific surface area of the catalyst D is 283m 2 (ii)/g; the pore volume was 0.36mL/g.
B. Hydrogenation reaction
Exactly the same as the hydrogenation process in example 1. The reactor outlet product components when catalyst D was employed: no alkyne and diene, and the content of monoolefine is 0.79wt%.
Example 5
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
The composite oxide support (designated as Z1) of example 1 was used.
b) Modification of the surface of a support
Preparing a cerium nitrate solution by using a volumetric flask, impregnating 100g of the carrier Z1 prepared in the step a) for 2 hours at normal temperature, drying for 4 hours at 110 ℃ after filtering, and roasting for 4 hours at 550 ℃ to finish the primary modification of the carrier Z1, wherein the carrier after the primary modification is marked as Z2.
Preparing a cobalt nitrate solution by using a volumetric flask, impregnating 100g of the carrier Z2 prepared in the step a) for 2 hours at normal temperature, filtering, drying at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to complete the modification of the carrier Z2, wherein the modified carrier is marked as Z3.
The cobalt oxide content in the Z3 carrier was 1.5wt%, and the cerium oxide content was 1.30wt%.
c) Loading of active ingredients
The same procedure as in example 1 was followed. To obtain MoO 3 MoO with a content of 14.1wt% and NiO with a content of 7.5wt% 3 -CoO/Al 2 O 3 -TiO 2 Catalyst E of (1).
The specific surface area of the catalyst E is 288m 2 (ii)/g; the pore volume was 0.37mL/g.
B. Hydrogenation reaction
Exactly the same as the hydrogenation process in example 1. The reactor outlet product component when catalyst E was employed: no alkyne and diene, the content of monoolefine is 0.73wt%.
Comparative example 1
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
The composite oxide support (designated as Z1) of example 1 was used.
b) Loading of active ingredients
MoO was obtained according to step c) of example 1 by loading the active ingredient on support Z1 3 MoO with a content of 14.1wt% and NiO with a content of 7.5wt% 3 -CoO/Al 2 O 3 -TiO 2 The catalyst a of (1).
B. Hydrogenation reaction
The same procedure as in example 1 was followed. The reactor outlet product components when catalyst I is employed: no alkyne and diene, the monoolefin content is 7.62wt%.
Comparative example 2
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
The composite oxide support (designated as Z1) of example 1 was used.
b) Modification of the surface of a support
Preparing a cerium nitrate solution by using a volumetric flask, impregnating 100g of the carrier Z1 prepared in the step a) for 2 hours at normal temperature, drying at 110 ℃ for 4 hours after filtering, and roasting at 550 ℃ for 4 hours to complete the modification of the carrier Z1, wherein the modified carrier is marked as Z2. The cerium oxide content in the Z2 carrier was 2.7wt%.
c) Loading of active ingredients
MoO was obtained by loading the active ingredient on the support Z2 in the manner of example 1 3 MoO with a content of 14.1wt% and NiO with a content of 7.5wt% 3 -CoO/Al 2 O 3 -TiO 2 The catalyst b of (1).
B. Hydrogenation reaction
Exactly the same as the hydrogenation process in example 1. The reactor outlet product component when catalyst b is used: no alkyne and diene, and the content of monoolefine is 3.62 percent by weight.
Comparative example 3
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
The composite oxide support (designated as Z1) of example 1 was used.
b) Modification of the surface of a support
Preparing a cobalt nitrate solution by using a volumetric flask, impregnating 100g of the carrier Z1 prepared in the step a) for 2 hours at normal temperature, filtering, drying at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to complete the modification of the carrier Z1, wherein the modified carrier is marked as Z2. The cobalt oxide content in the Z2 support was 2.7wt%.
c) Loading of active ingredients
MoO was prepared by supporting the active ingredient on support Z2 in the manner of example 1 3 MoO with a content of 14.1wt% and NiO of 7.5wt% 3 -CoO/Al 2 O 3 -TiO 2 Catalyst c according to (1).
B. Hydrogenation reaction
Exactly the same as the hydrogenation process in example 1. Reactor outlet product composition with catalyst c: no alkyne and diene, the content of monoolefine is 3.98wt%.
Comparative example 4
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
The composite oxide support (designated as Z1) of example 1 was used.
b) Modification of the surface of a support
Lanthanum nitrate was used in place of cerium nitrate in step b) of example 1, and the remaining conditions were identical, yielding a modified support, denoted Z2. The cobalt oxide content in the Z2 support was 1.2wt% and the lanthanum oxide content was 1.5wt%.
c) Loading of active ingredients
MoO was obtained by loading the active ingredient on the support Z2 in the manner of example 1 3 MoO with a content of 14.1wt% and NiO with a content of 7.5wt% 3 -CoO/Al 2 O 3 -TiO 2 Catalyst d of (1).
B. Hydrogenation reaction
Exactly the same as the hydrogenation process in example 1. The reactor outlet product components when catalyst d is employed: no alkyne and diene, and the content of monoolefine is 3.16wt%.
Comparative example 5
A. Preparation of hydrorefining catalyst
a) Using commercially available gamma-Al 2 O 3 The carrier has a performance index of a specific surface area of 330m 2 The pore volume is 0.46mL/g.
b) Modification of the surface of a support
Same as in example 1.
c) Loading of active ingredients
Same as in example 1. To obtain MoO 3 MoO with a content of 14.1wt% and NiO of 7.5wt% 3 -CoO/Al 2 O 3 Catalyst e of (3).
B. Hydrogenation reaction
The same procedure as in example 1 was followed. The reactor outlet product components when catalyst e is employed: no alkyne and diene, the monoolefin content is 17.8wt%.
Comparative example 6
A. Preparation of hydrorefining catalyst
a)Al 2 O 3 /TiO 2 Preparation of composite oxide support
The composite oxide support (designated as Z1) of example 1 was used.
b) Modified component and active component loading
Preparing a mixed solution of cobalt nitrate, cerium nitrate, ammonium molybdate tetrahydrate and nickel nitrate by using a volumetric flask, impregnating 100g of the carrier Z1 prepared in the step a) at normal temperature for 2 hours, filtering, drying at 110 ℃ overnight, and roasting at 550 ℃ for 4 hours to complete the loading of the modified component and the active component. The catalyst obtained is designated f. In the catalyst f, the content of cobalt oxide was 1.2wt%, the content of cerium oxide was 1.5wt%, and MoO 3 The content was 14.1wt%, and the content of NiO was 7.5wt%.
The specific surface area of the catalyst f is 286m 2 (iv) g; the pore volume was 0.36mL/g.
B. Hydrogenation reaction
The same procedure as in example 1 was followed. Reactor outlet product composition with catalyst f: no alkyne and diene, and mono-olefin content of 4.68wt%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A hydrorefining catalyst comprising Al 2 O 3 -TiO 2 Composite oxide and Al supported on the same 2 O 3 -TiO 2 The modified component comprises cobalt and/or cobalt oxide and cerium and/or cerium oxide, and the active component comprises molybdenum and/or molybdenum oxide and nickel and/or nickel oxide; preferably, with said Al 2 O 3 -TiO 2 The total mass of the composite oxide is calculated as the reference, al 2 O 3 The content of (A) is 70wt% -90 wt%; tiO 2 2 The content of (A) is 10wt% -30 wt%.
2. The hydrofinishing catalyst according to claim 1, wherein said hydrofinishing catalyst is prepared by pre-treating said Al 2 O 3 -TiO 2 The composite oxide is prepared by loading the modified component and then loading the active component; preferably, when the active component is loaded, molybdenum is loaded first, and then nickel is loaded.
3. Hydrofinishing catalyst according to claim 1 or 2, characterized in that the cobalt and/or cobalt oxide content is 0.5-2 wt%, calculated on the total mass of the hydrofinishing catalyst; the content of cerium and/or cerium oxide is 1-3 wt%; the content of molybdenum and/or molybdenum oxide is 8-20 wt%; the content of nickel and/or nickel oxide is 4wt% -12 wt%.
4. Hydrofinishing catalyst according to any one of claims 1 to 3, characterized in that it has a specific surface area of 150m 2 /g～400m 2 A/g, preferably of 150m 2 /g～300m 2 (ii)/g; the pore volume is 0.3 to 0.8mL/g, preferably 0.3 to 0.6mL/g.
5. A method for producing a hydrofinishing catalyst as claimed in any one of claims 1 to 4, comprising:
s1, adopting impregnating solution containing cobalt element and cerium element to treat Al 2 O 3 -TiO 2 Impregnating the composite oxide, drying and roasting a product obtained after impregnation to obtain the surface modified Al 2 O 3 -TiO 2 A composite oxide;
s2, adopting impregnation liquid containing molybdenum element to carry out surface modification on the Al 2 O 3 -TiO 2 Impregnating the composite oxide, and drying and roasting a product obtained after impregnation to obtain a catalyst precursor;
and S3, impregnating the catalyst precursor by using an impregnating solution containing a nickel element, and drying and roasting a product obtained after impregnation to obtain the hydrofining catalyst.
6. The preparation method according to claim 5, wherein in step S1, the roasting treatment conditions include a temperature of 450 ℃ to 650 ℃, preferably 500 ℃ to 600 ℃; the time is 1 to 24 hours, preferably 2 to 12 hours; and/or in step S2, the roasting treatment conditions comprise that the temperature is 450-650 ℃, preferably 500-600 ℃; the time is 1 to 24 hours, preferably 2 to 12 hours; and/or in the step S3, the roasting treatment conditions comprise that the temperature is 450-650 ℃, and preferably 500-600 ℃; the time is 1h to 24h, preferably 2h to 12h.
7. Use of a hydrofinishing catalyst according to any one of claims 1 to 4 or a hydrofinishing catalyst prepared by the process according to claim 5 or 6 in the field of catalysts for saturated hydrogenation, preferably in the field of catalysts for saturated hydrogenation of a fraction having a low content of diolefins, wherein the content of diolefins in the fraction having a low content of diolefins is not higher than 2wt%, preferably not higher than 1wt%.
8. C with low content of diolefin 4 A process for hydrogenating a distillate comprising: make C with low content of diolefin 4 Contacting the fraction with the hydrofining catalyst of any one of claims 1 to 4 or the hydrofining catalyst produced by the production method of claim 5 or 6, thereby treating the C with low diolefin content 4 Carrying out hydrogenation treatment on the fraction to prepare a hydrogenated product, wherein the content of the diolefin in the fraction with low content of diolefin is not higher than 2wt%, preferably not higher than 1wt%; more preferably, the fraction with low diolefin content has a content of monoolefin of 5-50 wt%.
9. The hydrogenation process of claim 8, wherein the contacting occurs in a reactor and the operating conditions of the reactor comprise: the pressure is 2.0MPa to 3.5MPa; the inlet temperature is 40-80 ℃; the volume space velocity is 0.3h -1 ～2.0h -1 (ii) a The volume ratio of the hydrogen to the fresh raw material is 30-300.
10. The hydrogenation process according to claim 8 or 9, wherein part of the hydrogenation product is recycled at a recycle ratio of 5 to 15.
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| CN102500403A (en) * | 2011-11-23 | 2012-06-20 | 武汉科林精细化工有限公司 | Liquefied gas hydrogenating, olefin content decreasing and desulfurizing catalyst and preparation method thereof |
| CN102861593A (en) * | 2011-07-06 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
| WO2018019203A1 (en) * | 2016-07-29 | 2018-02-01 | 武汉凯迪工程技术研究总院有限公司 | Boron-modified hydrofining catalyst having high loading amount and preparation method therefor |
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| CN102861593A (en) * | 2011-07-06 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN102500403A (en) * | 2011-11-23 | 2012-06-20 | 武汉科林精细化工有限公司 | Liquefied gas hydrogenating, olefin content decreasing and desulfurizing catalyst and preparation method thereof |
| WO2018019203A1 (en) * | 2016-07-29 | 2018-02-01 | 武汉凯迪工程技术研究总院有限公司 | Boron-modified hydrofining catalyst having high loading amount and preparation method therefor |
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