CN105536808B - A kind of hydrogenation catalyst and its preparation method and application - Google Patents
A kind of hydrogenation catalyst and its preparation method and application Download PDFInfo
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- CN105536808B CN105536808B CN201510993054.7A CN201510993054A CN105536808B CN 105536808 B CN105536808 B CN 105536808B CN 201510993054 A CN201510993054 A CN 201510993054A CN 105536808 B CN105536808 B CN 105536808B
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- maceration extract
- catalyst
- alumina
- hydrotreating
- hydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 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 40
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000000284 extract Substances 0.000 claims description 80
- 238000002803 maceration Methods 0.000 claims description 80
- 238000000034 method Methods 0.000 claims description 67
- 238000006555 catalytic reaction Methods 0.000 claims description 21
- 238000007598 dipping method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001802 infusion Methods 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 239000002671 adjuvant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000036541 health Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 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 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003915 liquefied petroleum gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052706 scandium Inorganic materials 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000004230 steam cracking Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- -1 is easy Coking Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- B01J23/888—Tungsten
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/888—Tungsten
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydrogenation catalysts and its preparation method and application.The hydrogenation catalyst includes carrier and active metal component, and the carrier is alumina-based supports, and active metal component is tungsten, molybdenum and nickel, and active metal component layer distributed, shell is Ni and Mo, and stratum nucleare is Ni and W.The features such as catalyst of the present invention is active high, stability is good and sulfur resistive toxicity is good, and when being used for low-carbon alkene hydrogenation reaction, unit capacity is big, and operation cycle is long.The hydrogenation catalyst is especially suitable for C8Following alkene plus hydrogen saturated reaction during.
Description
Technical field
The present invention relates to a kind of hydrogenation catalysts and its preparation method and application, specifically a kind of to be applied to C8Below
Catalyst of olefins hydrogenation and its preparation method and application is particularly suitable for C4Alkene adds hydrogen saturation.
Background technology
With the continuous improvement of the development of countries in the world petroleum refining industry, especially catalytic cracking technology, secondary operation device
Shared ratio is increasing in crude oil processing, and refinery gas resource is also more abundant therewith, the deep processing of refinery gas by
Gradually it is valued by people.Many refining ＆ chemical industry integration enterprises of China are in the prevalence of C4Fraction is superfluous, utilization rate is low asks
Topic.The C of refinery's by-product at present4Except on a small quantity by be etherified, be alkylated production high-knock rating gasoline blend component in addition to, remaining big portion
It is allocated as selling for oil liquefied gas product.Due to rising steadily for crude oil price, C4Economy value as conventional fuel sale
It must consider.In addition, natural gas being widely used in civilian and automobile-used market, the sale of refinery's liquefied gas will face huge choose
War.Therefore, how refinery by-product C is utilized4The downstream product for producing high added value, by the common concern of vast Petrochemical Enterprises.
By C4Fraction is a more feasible approach as preparing ethylene by steam cracking raw material, but these C4Alkene in fraction
Content is generally higher, and polymerization, cyclisation, condensation and coking reaction can occur in pyrolysis furnace for alkene, it is therefore necessary to remove alkene
It goes, it could be by C4Raw material of the fraction as preparing ethylene by steam cracking.
USP4059504 discloses a kind of tungsten oxide is added in nickel nitrate aqueous solution and is configured to co-impregnated solution, is supported on and compares table
Area is more than 150m2On/g aluminium oxide, through being air-dried, is roasted 3 hours at 457 DEG C, obtain hydrogenation catalyst.The catalyst
The low catalyst activity that causes of specific surface area is low, and therefore, when handling drippolene, colloid easily attachment on a catalyst, is easy
Coking, catalyst life are shorter.
CN200810238973.3 discloses one kind using aluminium oxide as carrier, and active component is the hydrogenation catalyst of precious metal palladium
Agent, select it is one or more in auxiliary agent B, one or more and Ag, Pb, Au, Co, Cu, Bi, Ni, Pt, Ti in P, Si, together
When alkali metal and/or alkaline-earth metal is added, catalyst is suitable for catalytic cracking process and preparing ethylene by steam cracking byproduct in process
C4Fraction adds hydrogen saturation, but therefore catalyst preparation process is complex, and cost is also higher, while as noble metal catalyst
It is very easy to poisoning, and the liquid air speed of hydrogenation reaction is relatively low（0. 5~3.0h-1）.
Invention content
In order to overcome shortcoming in the prior art, the present invention provides one kind plus hydrogen saturated activity height, stability are good
The good hydrogenation catalyst and preparation method thereof with sulfur resistive toxicity, the present invention also provides the application of the catalyst, the catalyst energy
It is enough in C8Following olefins hydrogenation, especially suitable for containing C4Olefin feed adds hydrogen to produce ethylene cracking material.
The hydrogenation catalyst of the present invention, including carrier and active metal component, the carrier is alumina-based supports, living
Property metal component be tungsten, molybdenum and nickel, active metal component layer distributed, shell be Ni and Mo, stratum nucleare be Ni and W.
The hydrogenation catalyst of the present invention, on the basis of the weight of catalyst, oxidation molybdenum content is 5wt%~40wt%, oxidation
W content is 5wt%~30wt%, and nickel oxide content is 2wt%~20wt%, and vector contg is 50wt%~80wt%.
The hydrogenation catalyst of the present invention, on the basis of the weight of catalyst, molybdenum oxide is 10wt%~21wt%, and nickel oxide is
2wt%~11wt%, tungsten oxide are 5wt%~20wt%, and vector contg is 50wt%~80wt%.
In the hydrogenation catalyst of the present invention, molar ratios of the Ni preferably in shell and stratum nucleare is 3~7：7~3, preferably 5
~7：5~3.
In the hydrogenation catalyst of the present invention, co-catalysis component can be contained, wherein co-catalysis group is divided into Y, La, Sc, Ce
One or more, preferably one or more in La, Sc, Ce, co-catalysis component containing in the catalyst in terms of oxide
Amount is 6wt% or less.Molar ratio of the co-catalysis component preferably in the shell and stratum nucleare in hydrogenation catalyst is 3~7：7：3,
Further preferably 5~7：5~3.
The property of the hydrogenation catalyst of the present invention is as follows：Specific surface area is 100~250m2/ g, Kong Rongwei 0.3~0.6
mL/g。
In the hydrogenation catalyst of the present invention, alumina-based supports refer to the carrier using aluminium oxide as key component, can be with
Containing one or more in adjuvant component, such as group ia, group iia metallic element, one preferably in potassium, magnesium, calcium, barium
Kind is a variety of.Content of the adjuvant component in terms of oxide in alumina-based supports accounts for 10wt% hereinafter, preferably 6 wt% or less.
Alumina-based supports are preferably tooth spherical shape.
The preparation method of hydrogenation catalyst of the present invention, preparation process include：
（1）The preparation of alumina-based supports；
（2）Maceration extract is prepared, wherein the first maceration extract is the maceration extract of tungstenic, and second of maceration extract is the dipping containing molybdenum
Liquid；
（3）Alumina-based supports impregnate the first maceration extract using vacuum-impregnated method, obtain intermediate,
（4）Step（3）The intermediate of gained impregnates second of maceration extract using the method for saturation dipping, through dry and roasting
It burns, obtains hydrogenation catalyst；
Wherein, it is as follows to be introduced into the method in catalyst for nickel：
Method one is individually prepared nickeliferous maceration extract and is loaded in alumina-based supports using infusion process, then carried out again
Step（2）And step（3）The method of the first maceration extract and second of maceration extract is impregnated successively；
Method two individually prepares nickeliferous maceration extract, first carries out step（2）And step（3）, then use infusion process to use again
Nickeliferous maceration extract impregnation steps（3）The product obtained through dry and roasting；
Method three, the method in the first maceration extract and second of maceration extract is added to by nickel, and oxygen is loaded to simultaneously with tungsten, molybdenum
Change on alumina-based support；
Method four can also use above two or a variety of methods to be combined.
In method one, method two or method four, when dip loading independent using nickel, after dipping, dry and roasting need to be passed through
It is the step of burning, i.e., 2~14 hours dry at 20~100 DEG C in air atmosphere, it is roasted 2~8 hours at 400~700 DEG C.
In the preparation method of hydrogenation catalyst of the present invention, it is as follows that co-catalysis component is introduced into the method in catalyst：
Method A individually prepares the maceration extract of maceration extract or preparation containing co-catalysis component and nickel of the component containing co-catalysis,
It is loaded in alumina-based supports using infusion process, then carries out step again（2）And step（3）The first dipping is impregnated successively
The method of liquid and second of maceration extract；
Method B individually prepares the maceration extract of maceration extract or preparation containing co-catalysis component and nickel of the component containing co-catalysis,
First carry out step（2）And step（3）, the maceration extract impregnation steps of infusion process component containing co-catalysis and nickel are then used again（3）
The product obtained through dry and roasting；
Co-catalysis component is added to the method in the first maceration extract and second of maceration extract by method C, simultaneously with tungsten, molybdenum
It loads in alumina-based supports；
Method D can also use above two or a variety of methods to be combined；
In method A, method B or method D, contain co-catalysis group when using the independent dip loading of co-catalysis component or using
When dividing the maceration extract dip loading with nickel, after dipping, the step of drying need to be passed through and roasted, i.e., 20~100 in air atmosphere
It is 2~14 hours dry at DEG C, it is roasted 2~8 hours at 400~700 DEG C.
Step（1）In, alumina-based supports refer to the carrier using aluminium oxide as key component, can also contain auxiliary agent group
Point, such as it is one or more in group ia, group iia metallic element, it is preferably one or more in potassium, magnesium, calcium, barium.
Content of the adjuvant component in terms of oxide in alumina-based supports accounts for 10wt% hereinafter, preferably 6 wt% or less.Alumina base
Carrier is preferably tooth spherical shape.The tooth spherical alumina support preparation process may be used existing method and prepare, such as referring to
Method etc. described in CN200910079772.8.
Step（2）In, the method for maceration extract is prepared using conventional preparation method, according to active metal in catalyst and is helped
The content of catalyst component and the adsorbance of carrier, and the first maceration extract, second of maceration extract, nickeliferous is prepared as needed
The maceration extract of maceration extract, the maceration extract of the component containing co-catalysis and component containing co-catalysis and nickel.
Step（3）In, vacuum unsaturation infusion process, the use of the first maceration extract may be used in the vacuum-impregnated method
Amount for saturation dipping when required maceration extract dosage by volume 0.3~0.9, preferably 0.4~0.7, detailed process is as follows：It will
Step（1）Carrier obtained is placed in vacuum filtration bottle, and step is added（2）The first maceration extract obtained is filtered by vacuum, and filters
Pressure ≮ 0.08MPa, preferably 0.08~0.15MPa are filtered to maceration extract and are all adsorbed.Taking-up is placed on health in pallet
（It is placed in room temperature and is protected from light place）0.5~5.0 hour；
Step（4）In, the drying condition is dried 2~14 hours at 20~100 DEG C in air atmosphere, described
Roasting condition is：It is roasted 2~6 hours in 350~650 DEG C of air atmospheres.
In the method for the present invention, the volume calculation formula of maceration extract is：VMaceration extract=mCarrier/ρCarrier（VMaceration extractFor maceration extract volume, mCarrier
To dry back loading carrier quality, ρCarrierFor the heap density of carrier after drying）
The present invention also provides a kind of application process of hydrogenation catalyst of the present invention, catalyst of the present invention is applied to C8Below
In the hydrogenation technique of alkene, especially C4In the hydrogenation technique of alkene, preferable process conditions are：Hydrogen Vapor Pressure 1.5~
3.0MPa, hydrogen to oil volume ratio 100：1~400：1, reaction temperature is 30~150 DEG C, and volume space velocity is 2~10h when liquid-1, excellent
It is selected as 5~10h-1.The catalyst needs in presence of hydrogen before use, at 150~450 DEG C, at preferably 200~380 DEG C, and reduction
4~10 hours.
In hydrogenation catalyst of the present invention, active metal component layer distributed, shell is Ni and Mo, and stratum nucleare is Ni and W, with list
Pure nickel-loaded catalyst is compared, active higher, and compared with the noble metal catalysts such as supported palladium, sulfur resistive toxicity is more preferable.The present invention's adds
Hydrogen catalyst has plus hydrogen saturated activity is high, stability is good, sulfur resistive toxicity is good, especially suitable for low-carbon alkene plus hydrogen saturated reaction
In, the treating capacity of device can also be improved.
The method that the present invention is combined using vacuum impregnation and saturation dipping, it is in layer distributed, i.e. shell to make active metal
For Ni and Mo, stratum nucleare is Ni and W, can make preferably to coordinate between active component, while between active component and auxiliary agent, carrier
Preferably matching, improves the comprehensive performance of hydrogenation catalyst.Catalyst prepared by the method for the present invention is suitable for C8Following alkene adds
Hydrogen saturated reaction process especially is used to handle the C of catalytic cracking unit4The C of fraction and preparing ethylene by steam cracking device4Fraction,
Add hydrogen saturated activity higher, olefin(e) centent can be obtained<The hydrofinishing product of 0.5v%, and the processing of device is big, stablizes fortune
It is long to turn the time.
Specific implementation mode
Below by embodiment, the present invention is further described, but is not intended to limit the present invention.Catalyst uses one section
Fixed bed hydrogenation reactor carries out catalyst activity and estimation of stability, and reactor is using stainless steel axial flow reactor, internal diameter
16mm is highly 80cm, and reactor exterior circumferential uses electrical heating constant temperature.By the catalyst prepared and inert carrier（Volume
Than being 1：1）Mixing is fitted into reactor, and slowly heating carries out selective hydrogenation reaction.
Embodiment 1
（1）Tooth spherical alumina support is prepared, property is as follows：Specific surface area is 240m2/ g, Kong Rongwei 0.45mL/g；
（2）Prepare maceration extract, wherein the first maceration extract is the maceration extract of nickeliferous, tungsten and lanthanum, second maceration extract be containing
The maceration extract of nickel, molybdenum and lanthanum；In two kinds of maceration extracts, the dosage of nickel makes its molar ratio in the shell and stratum nucleare of catalyst be
6：4；The dosage of lanthanum makes its molar ratio in the shell and stratum nucleare of catalyst be 6：4；
（3）By step（1）Carrier obtained is placed in vacuum filtration bottle, and step is added（2）The first maceration extract obtained,
When the dosage of the first maceration extract is saturation dipping maceration extract dosage by volume 0.6, vacuum filtration, filtering pressure is
0.09MPa is filtered to maceration extract and is all adsorbed.Taking-up is placed on health in pallet（It is placed in room temperature and is protected from light place）3.0 hour；
（4）Step（3）The intermediate of gained impregnates second of maceration extract using the method for saturation dipping, in air atmosphere
It is 6 hours dry at 80 DEG C, it is roasted 4 hours in 480 DEG C of air atmospheres, obtains hydrogenation catalyst A.
In catalyst A, the content of tungsten oxide is 6 wt%, and the content of molybdenum oxide is 10 wt%, and the content of nickel oxide is 5
The content of wt%, auxiliary agent lanthana are 0.5wt%.The catalyst is reacted for hydrogenation of liquefied petroleum gas, after reacting 200 hours, is taken
Sample analyzes product composition, and wherein operating condition and reaction result is shown in Table 1.
Embodiment 2
The present embodiment prepares catalyst B.
The preparation of catalyst B is the same as embodiment 1, difference：The first maceration extract is the maceration extract of nickeliferous, tungsten and scandium, the
Two kinds of maceration extracts are the maceration extract of nickeliferous, molybdenum and scandium；In two kinds of maceration extracts, the dosage of nickel makes it in the shell and core of catalyst
Molar ratio in layer is 5.5：4.5；The dosage of scandium makes its molar ratio in the shell and stratum nucleare of catalyst be 5.5：4.5.
In catalyst B, the content of molybdenum oxide is 15wt%, and the content of tungsten oxide is 8wt%, and the content of nickel oxide is 3 wt%,
The content of auxiliary agent scandium oxide is 0.9 wt%.The catalyst is reacted for hydrogenation of liquefied petroleum gas, after reacting 200 hours, sampling
Product composition is analyzed, wherein operating condition and reaction result is shown in Table 1.
Embodiment 3
The present embodiment prepares catalyst C.
The preparation of catalyst C is the same as embodiment 1, difference：The first maceration extract is the maceration extract of nickeliferous, tungsten and cerium, the
Two kinds of maceration extracts are the maceration extract of nickeliferous, molybdenum and cerium；In two kinds of maceration extracts, the dosage of nickel makes it in the shell and core of catalyst
Molar ratio in layer is 6.5：3.5；The dosage of cerium makes its molar ratio in the shell and stratum nucleare of catalyst be 6：4.
In catalyst C, the content of molybdenum oxide is 12wt%, and the content of tungsten oxide is 5wt%, and the content of nickel oxide is 3 wt%,
The content of auxiliary agent cerium oxide is 1.0 wt%.The catalyst is reacted for hydrogenation of liquefied petroleum gas, after reacting 200 hours, sampling
Product composition is analyzed, wherein operating condition and reaction result is shown in Table 1.
Comparative example 1
Comparative example 1 is using conventional preparation catalyst DA.
Using the tooth spherical alumina support in embodiment 1.Formed by 1 catalyst of embodiment prepare maceration extract is nickeliferous, molybdenum,
The maceration extract of tungsten and lanthanum, it is then 6 hours dry at 80 DEG C in air atmosphere using saturation dip loading, in 480 DEG C of air
It is roasted 4 hours in atmosphere, obtains hydrogenation catalyst DA.
In catalyst DA, the content of tungsten oxide is 6 wt%, and the content of molybdenum oxide is 10wt%, and the content of nickel oxide is 5
The content of wt%, auxiliary agent lanthana are 0.5wt%.The catalyst is reacted for hydrogenation of liquefied petroleum gas, after reacting 200 hours, is taken
Sample analyzes product composition, and wherein operating condition and reaction result is shown in Table 1.
Comparative example 2
Catalyst DB is made in this comparative example.
As described in Example 1, the first maceration extract is only replaced with second of maceration extract to catalyst DB by difference,
Second of maceration extract replaces with the first maceration extract.
In catalyst DB, the content of tungsten oxide is 6wt%, and the content of molybdenum oxide is 10wt%, and the content of nickel oxide is 5wt%,
The content of auxiliary agent lanthana is 0.5wt%.The catalyst is reacted for hydrogenation of liquefied petroleum gas, after reacting 200 hours, sampling point
Division object forms, and wherein operating condition and reaction result is shown in Table 1.
1 hydrogenation reaction raw material of table, product characteristics and reaction condition
| Project | Raw material | Embodiment 1 | Embodiment 2 |
| Operating condition | |||
| Hydrogen Vapor Pressure, MPa | 2.2 | 2.1 | |
| Inlet temperature, DEG C | 64 | 52 | |
| Volume space velocity when liquid, h-1 | 10 | 8 | |
| Hydrogen to oil volume ratio | 120 | 150 | |
| Composition, v% | |||
| Iso-butane | 42.8 | 44.8 | 46.0 |
| Normal butane | 32.9 | 54.7 | 53.6 |
| Anti- butylene | 7.4 | 0.09 | 0.08 |
| Butene-1 | 10.6 | 0.03 | 0.03 |
| Isobutene | 1.5 | 0.02 | 0.02 |
| Maleic | 4.6 | 0.06 | 0.04 |
| Butylene is total | 24.1 | 0.29 | 0.17 |
| Alkene saturation factor, v% | 99.2 | 99.3 | |
| Determination of Alkane Content, v% | 99.7 | ~100 | |
| Hydrogenation selectivity, % | 99.7 | 99.8 |
Table 1（It is continuous）
| Project | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Operating condition | |||
| Hydrogen Vapor Pressure, MPa | 2.1 | 2.1 | 2.1 |
| Inlet temperature, DEG C | 41 | 41 | 41 |
| Volume space velocity when liquid, h-1 | 10 | 10 | 9 |
| Hydrogen to oil volume ratio | 120 | 120 | 120 |
| Composition, v% | |||
| Iso-butane | 45.3 | 43.0 | 42.3 |
| Normal butane | 54.3 | 46.2 | 45.4 |
| Anti- butylene | 0.05 | 2.40 | 3.4 |
| Butene-1 | 0.04 | 4.60 | 5.5 |
| Isobutene | 0.02 | 0.84 | 0.96 |
| Maleic | 0.04 | 0.76 | 0.46 |
| Butylene is total | 0.15 | 8.60 | 10.32 |
| Alkene saturation factor, v% | 99.7 | 63.4 | 57.2 |
| Determination of Alkane Content, v% | 99.8 | 91.20 | 89.47 |
| Hydrogenation selectivity, % | ~100 |
Note：In raw material, 130 μ g/g of sulfur content；0.035 μ g/g of arsenic content.
Claims (13)
1. a kind of method of hydrotreating of low-carbon alkene, which is characterized in that the low-carbon alkene hydrogenation catalyst of use, including carrier and work
Property metal component, the carrier be alumina-based supports, active metal component be tungsten, molybdenum and nickel, active metal component layering
Distribution, shell are Ni and Mo, and stratum nucleare is Ni and W；In the hydrogenation catalyst, molar ratios of the Ni in shell and stratum nucleare is 5
~7：5~3 and include 5：5；In the hydrogenation catalyst, containing co-catalysis component, wherein co-catalysis group be divided into Y, La,
One or more in Sc, Ce, content of the co-catalysis component in terms of oxide in the catalyst is 6wt% or less；Co-catalysis group
The molar ratio divided in shell and stratum nucleare is 5~7：5~3 and include 5：5；
On the basis of the weight of catalyst, oxidation molybdenum content is 5wt%~40wt%, and tungsten oxide content is 5wt%~30wt%,
Nickel oxide content is 2wt%~20wt%, and vector contg is 50wt%~80wt%；
Low-carbon alkene adds process conditions used by hydrogen to be：1.5~3.0MPa of Hydrogen Vapor Pressure, hydrogen to oil volume ratio 100：1~
400：1, reaction temperature is 30~150 DEG C, and volume space velocity is 2~10h when liquid-1；
Hydrogenation catalyst needs to restore in presence of hydrogen before use, and reducing condition is as follows：At 150~450 DEG C, reduction 4~
10 hours.
2. method of hydrotreating described in accordance with the claim 1, it is characterised in that：On the basis of the weight of catalyst, molybdenum oxide is
10wt%~21wt%, nickel oxide be 2wt%~11wt%, tungsten oxide be 5wt%~20wt%, vector contg be 50wt%~
80wt%.
3. method of hydrotreating described in accordance with the claim 1, it is characterised in that：The property of the hydrogenation catalyst is as follows：Specific surface
Product is 100~250m20.3~0.6mL/g of/g, Kong Rongwei.
4. method of hydrotreating described in accordance with the claim 1, it is characterised in that：In the hydrogenation catalyst, alumina-based supports are
Refer to using aluminium oxide as the carrier of key component, in alumina-based supports content of the adjuvant component in terms of oxide account for 10wt% with
Under, adjuvant component is one or more in group ia, group iia metallic element.
5. method of hydrotreating described in accordance with the claim 1, it is characterised in that：The alumina-based supports are that tooth is spherical.
6. method of hydrotreating described in accordance with the claim 1, it is characterised in that：The preparation method of the hydrogenation catalyst, prepared
Journey includes：
(1) preparation of alumina-based supports；
(2) maceration extract is prepared, wherein the first maceration extract is the maceration extract of tungstenic, and second of maceration extract is the maceration extract containing molybdenum；
(3) alumina-based supports impregnate the first maceration extract using vacuum-impregnated method, obtain intermediate,
(4) intermediate obtained by step (3) impregnates second of maceration extract using the method for saturation dipping, through dry and roasting, obtains
To hydrogenation catalyst；
Wherein, it is as follows to be introduced into the method in catalyst for nickel：
Nickel is added to the method in the first maceration extract and second of maceration extract, alumina-based supports are loaded to simultaneously with tungsten, molybdenum
On；
Wherein, it is as follows to be introduced into the method in catalyst for co-catalysis component：
Co-catalysis component is added to the method in the first maceration extract and second of maceration extract, oxidation is loaded to simultaneously with tungsten, molybdenum
On alumina-based support.
7. method of hydrotreating according to claim 6, it is characterised in that：In step (3), the vacuum-impregnated method uses
Vacuum unsaturation infusion process, the dosage of the first maceration extract when being saturation dipping required maceration extract dosage by volume 0.3~
0.9, detailed process is as follows：Carrier made from step (1) is placed in vacuum filtration bottle, the first made from step (2) is added
Maceration extract, vacuum filtration filter pressure ≮ 0.08MPa, filter to maceration extract and all adsorb, health 0.5~5.0 is small after taking-up
When；In step (4), the drying condition is 2~14 hours dry at 20~100 DEG C in air atmosphere, the roasting
Condition is：It is roasted 2~6 hours in 350~650 DEG C of air atmospheres.
8. method of hydrotreating according to claim 7, it is characterised in that：In step (3), vacuum unsaturation dipping
Method, the dosage of the first maceration extract when being saturation dipping required maceration extract dosage by volume 0.4~0.7.
9. method of hydrotreating according to claim 7, it is characterised in that：The vacuum filtration, filter pressure be 0.08~
0.15MPa。
10. method of hydrotreating described in accordance with the claim 1, it is characterised in that：Low-carbon alkene is C8Following alkene.
11. method of hydrotreating described in accordance with the claim 1, it is characterised in that：Low-carbon alkene is C4Alkene.
12. method of hydrotreating described in accordance with the claim 1, it is characterised in that：Volume space velocity is 5~10h when the described liquid-1。
13. method of hydrotreating described in accordance with the claim 1, it is characterised in that：The reduction item is as follows：At 200~380 DEG C
Under, it restores 4~10 hours.
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| CN111905745B (en) * | 2020-08-06 | 2022-01-04 | 中国科学院过程工程研究所 | A kind of nickel-based catalyst for methyl acrylate hydrogenation reaction and method thereof |
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| CN102343270A (en) * | 2010-07-28 | 2012-02-08 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal components in layered distribution and preparation method thereof |
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