CN106925288A - A kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst - Google Patents
A kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst Download PDFInfo
- Publication number
- CN106925288A CN106925288A CN201710069386.5A CN201710069386A CN106925288A CN 106925288 A CN106925288 A CN 106925288A CN 201710069386 A CN201710069386 A CN 201710069386A CN 106925288 A CN106925288 A CN 106925288A
- Authority
- CN
- China
- Prior art keywords
- powder
- catalyst
- solution
- modified
- peg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000000843 powder Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 9
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000007603 infrared drying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 4
- 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 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 abstract description 6
- 230000023556 desulfurization Effects 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 2
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 56
- 239000011148 porous material Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J23/70—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
- B01J23/8885—Tungsten containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
It is modified the preparation method of Ni-based ternary unsupported catalyst the present invention relates to a kind of auxiliary agent PEG and SB powder that adds, it is two kinds of different auxiliary agents of introducing during coprecipitation prepares unsupported catalyst, active component, auxiliary agent are combined, i.e., PEG the and SB powder of different molecular weight is added in nickel molybdate and ammonium metatungstate mixed solution respectively as dispersant surfactants and dispersant.Modified unsupported catalyst preparation method of the present invention, the dispersiveness of active metal component and the Hydrogenation of catalyst can be effectively improved, the mechanical strength of unsupported catalyst is significantly improved, while ensure that modified catalyst meets strict demand of the GB to diesel deep desulfurization after the hydrogenation reaction.
Description
Technical field
The present invention relates to the preparation field of catalyst, specifically a kind of addition auxiliary agent PEG and SB powder Ni-based ternary that is modified is non-
The preparation method of loaded catalyst.
Background technology
In the preparation process of unsupported catalyst, addition auxiliary agent is conducive to improving hydrodesulfurization, the denitrogenation of catalyst
Activity, this is mainly manifested in some auxiliary agents can play a part of pore-creating, enrich catalyst pore structure, such as some surface-actives
Agent etc..In addition, auxiliary agent may also function as the effect of dispersed active metal component, the middle strong acid quantity of catalyst is improved.It is mature and stable
Diesel fuel desulfurization catalyst activity, it is acid, reclaim the problems such as on have a strict requirements, auxiliary agent is can not in catalyst research and development
The important component for lacking.Two kinds of current Hydrobon catalyst basic load type catalyst and unsupported catalyst；Its
Active component industrially using more, is often carried on γ-Al by middle loaded catalyst2O3Or on the carrier such as molecular sieve,
Loaded catalyst is obtained final product through steps such as drying, roasting, shapings again, but loaded catalyst has the shortcomings that itself cannot overcome,
As catalyst is influenceed by the limitation of active metal load capacity and carrier, active metal density is smaller, activated centre not enough collects
Medium, hydrogenation activity is subject to a definite limitation.Therefore, the concern in recent years to non-supported hydrogenation desulphurization catalyst increasingly increases,
Research deepens continuously, many gratifying achievement of acquirement.This kind of non-loading type is described in United States Patent (USP) US 6299760B1 to urge
Agent prepares the composite oxide of metal with suitable specific surface area, meso-hole structure using solid surface reaction technology, through pre-
Vulcanization, prepares non-negative supported metal sulphide hydrogenation catalyst.The B of Chinese invention patent CN 103801316 describe a kind of logical
The presoma that coprecipitation prepares composite oxides is crossed, and macromolecular PEG is introduced in precipitation process, obtained in the middle of catalyst
Body, is impregnated with specific maceration extract and obtains hydrogenation catalyst.Chinese invention patent CN 101172261A describe one kind and prepare
W-Mo-Ni non-supported hydrogenation catalysts, the catalyst using active metal Ni, W component and auxiliary agent saline mixed solution with
Sodium metaaluminate co-precipitation production composite oxides presoma, supporting for active metal is unrestricted, it is possible to provide more activity gold
Category total amount.
But catalyst described above itself also all has some defects, such as catalytic mechanical intensity is poor, preparation process
Middle metal recovery rate is low, on the high side etc..Therefore, it is necessary to a kind of new preparation method is developed, so as to improve non-loading type urge
The performance of agent.
The content of the invention
Divide it is an object of the invention to catalyst metals active component in improving existing unsupported catalyst technology of preparing
Scattered property is poor, pore structure is not flourishing enough, the shortcoming of bad mechanical strength.Increase catalytic metal utilization rate, improves its hydrogenation reaction
Activity.
The purpose of the present invention is achieved through the following technical solutions：
A kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst, and preparation process includes：
(1) Mo, W ammonium salt of 0.02-0.1mol are weighed, 300 ml deionized water wiring solution-forming A is dissolved in, and adjust molten with precipitating reagent
Liquid A is to appropriate pH value；
(2) water soluble nickel salt of 0.05-0.2mol is weighed for co-catalysis component raw material, is dissolved in 25 ml deionized water wiring solution-formings
B；
(3) solution A is added to mix solution B, it is seen that to have precipitation to generate, suspension of the stirring containing precipitation at 70-100 DEG C
3-8 h, add 0.02-0.1 mol PEG, 0.02-0.1 mol SB powder in whipping process, make active component compound complete, stir
Constant temperature stands solution after the completion of mixing, and burin-in process 4-18 h are carried out to it；
(4) ageing process terminates rear suction filtration suspension, and washs filter cake with deionized water, and filter cake is placed in into constant temperature infra-red drying
4-32 h are dried in case, catalyst precursor is obtained；
(5) reduction obtains final product the unsupported catalyst with good hydrodesulfurization activity in fired, device.
Wherein, selected water soluble nickel salt can be Nickelous nitrate hexahydrate, nickel acetate tetrahydrate, Nickel dichloride hexahydrate,
One kind in nickel sulfate, two kinds of group vib metallic compounds are any two kinds in the ammonium salt of Mo, W or Cr.
Wherein, the metal molar proportioning of co-catalysis component Ni and two kinds of group vib active components is water soluble nickel salt：Seven molybdic acids
Ammonium：Ammonium metatungstate=1: 1~4：1~4.
Wherein, selected precipitating reagent is the one kind in ammoniacal liquor, sodium carbonate, sodium acid carbonate and NaOH.
Wherein, it is to be added dropwise over or disposably add that solution B adds the mode of solution A, when being added dropwise over, using equality of temperature or
Different temperature is added dropwise；It is to be slowly added into or disposably add that PEG adds the mode of solution, when being slowly added into, is fallen using equality of temperature or different temperature
Enter；It is to be slowly added into or disposably add that SB powder adds the mode of solution, when being slowly added into, is poured into using equality of temperature or different temperature.
Wherein, the aging time described in step (3) is 6-10 h.
Wherein, calcination process is carried out to catalyst precursor, sintering temperature is 300-500 DEG C, and roasting time is 2-6 h,
Roasting obtains corresponding oxidized catalyst after terminating；Reversion in device is carried out to oxidized catalyst, reduction pressure is 2-4
MPa, temperature is 200-400 DEG C, and air speed is 1-4 h-1, hydrogen to oil volume ratio is 200-700, and the recovery time is 4-24 h, is reduced
Journey obtains corresponding sulphided state catalyst after terminating.
Wherein, the molecular weight of described PEG is 100-10000.
Wherein, the addition of described SB powder accounts for the 10%-30% of catalyst gross mass.
Compared with existing conventional unsupported catalyst preparation method, there is advantages below than the present invention：
(1) specific surface area of ternary metal unsupported catalyst prepared by the present invention is 70-120 m2/ g, pore volume is 0.15-
0.19cm3/ g, average pore size is 5.6-6.7 nm.The catalyst particle size is fine, and rate of metal is high, adds with preferable
Hydrogen desulphurization reaction activity.The preparation process of catalyst is simple, easy to operate, and preparation condition is gentle, beneficial to industrialized production and application.
(2) non-loading type Ni bases catalyst prepared by the present invention reacts for diesel hydrogenation for removal sulphur, improves vulcanization in diesel oil
The removal efficiency of thing.The sulfide molecules in diesel oil is at utmost changed into hydrogen sulfide by catalytic hydrogenation reaction, significantly improve
Diesel fuel desulfurization rate, meets increasingly strict diesel oil sulfur content national standard.
(3) existing conventional unsupported catalyst preparation method is contrasted, the significant technical characteristic of the present invention is coprecipitated
Shallow lake method selects suitable nickel source during preparing unsupported catalyst, and introduces two kinds of auxiliary agents respectively.By two kinds of auxiliary agents
Addition cause that prepared unsupported catalyst particle is uniform, arrangement regulation is neat, pore structure is more flourishing, metal profit
Accordingly increased with rate, hydrodesulfurization activity is significantly improved, desulfurization degree is close to 100%.
(4) while, operability of the present invention is very strong, and preparation condition is gentle, is suitable to batch and amplifies that produce and industrialize should
With.
Brief description of the drawings
Fig. 1 is the pattern schematic diagram of the gained catalyst of the embodiment of the present invention 2.
Specific embodiment
The present invention is described in further details with reference to embodiment, but protection scope of the present invention does not receive embodiment institute
Limit.
Embodiment 1
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs the g of nickel acetate tetrahydrate 9.954, the g of ammonium heptamolybdate 5.071, partially
The g of ammonium tungstate 3.531.The g of ammonium heptamolybdate 5.071, the g of ammonium metatungstate 3.531 are poured into the there-necked flask of 500 ml capacity, with 300
The deionized water of ml is completely dissolved at 50 DEG C, obtains solution A.The pH=9 of solution A, water are adjusted as precipitating reagent with ammoniacal liquor
Bath heated solution A temperature is to 90 DEG C.Nickel acetate tetrahydrate is poured into beaker with 20 ml deionized water dissolvings, solution B is obtained.
Solution B is changed in slow instillation solution A under equality of temperature, it is seen that there is precipitation to increasingly generate.After after completion of dropping, stir molten at 90 DEG C
The h of liquid 5, makes active component fully be combined.The g of PEG 1.856 g, SB powder 1.523 is separately added into solution in whipping process, waits to stir
Mix after finishing, stand suspension to carry out it hydrothermal aging treatment, the h of ageing time 2.Suction filtration suspension, washes after aging end
Wash filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 120 DEG C, catalyst precursor is obtained.Presoma is entered
Row roasting, 450 DEG C of sintering temperature, the h of roasting time 4 obtains oxidized catalyst.Compressing tablet, sieving are carried out to calcined catalyst,
Choose 20-40 mesh particle and load reactor.In 4 MPa, 350 DEG C, 2 h-1, catalyst is carried out in device under conditions of G/L=500
Reversion, gained specific surface area of catalyst is 77 m2/ g, pore volume 0.15cm3/ g, the nm of average pore size 5.6.
Embodiment 2
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs the g of Nickelous nitrate hexahydrate 11.632, the g of ammonium heptamolybdate 5.071,
The g of ammonium metatungstate 3.531.Mo, W compound are poured into the there-necked flask of 500 ml capacity, with the deionized water of 300 ml 50
It is completely dissolved at DEG C, is obtained solution A.The pH=9 of solution A is adjusted as precipitating reagent with ammoniacal liquor, heating water bath solution A temperature is extremely
90 ℃.Nickelous nitrate hexahydrate is poured into beaker with 20 ml deionized water dissolvings, solution B is obtained.Solution B is changed slowly under equality of temperature
In instillation solution A, it is seen that there is precipitation to increasingly generate.After after completion of dropping, the h of agitating solution 5 at 90 DEG C fills active component
Divide compound.The g of PEG 2.023 g, SB powder 4.047 is separately added into solution in whipping process, it is to be mixed finish after, stand and suspend
Liquid is carrying out hydrothermal aging treatment, the h of ageing time 2 to it.Suction filtration suspension after aging end, washs filter cake.Filter cake is placed in
In infrared drying oven, 12 h are dried at 110 DEG C, catalyst precursor is obtained.Presoma is calcined, sintering temperature 450
DEG C, the h of roasting time 4 obtains oxidized catalyst.Compressing tablet, sieving are carried out to calcined catalyst, 20-40 mesh particle is chosen and is loaded
Reactor.In 4 MPa, 360 DEG C, 2 h-1, reversion in device, gained catalyst are carried out to catalyst under conditions of G/L=500
Specific surface area is 86 m2/ g, the cm of pore volume 0.153/ g, the nm of average pore size 5.8.
Embodiment 3
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs the g of Nickel dichloride hexahydrate 9.520, the g of ammonium heptamolybdate 5.071, partially
The g of ammonium tungstate 3.531.Mo, W compound are poured into the there-necked flask of 500 ml capacity, with the deionized water of 300 ml at 50 DEG C
It is completely dissolved, is obtained solution A.The pH=9 of solution A, heating water bath solution A temperature to 90 are adjusted as precipitating reagent with ammoniacal liquor
℃.Nickel dichloride hexahydrate is poured into beaker with 20 ml deionized water dissolvings, solution B is obtained.Solution B is slowly dripped under equality of temperature
In entering solution A, it is seen that there is precipitation to increasingly generate.After after completion of dropping, the h of agitating solution 5 at 90 DEG C makes active component abundant
It is compound.The g of PEG 1.812 g, SB powder 3.624 is separately added into solution in whipping process, it is to be mixed finish after, stand suspension
To carry out burin-in process, the h of ageing time 4 to it.Suction filtration suspension after aging end, washs filter cake.Filter cake is placed in infrared dry
In dry case, 12 h are dried at 110 DEG C, catalyst precursor is obtained.Presoma is calcined, 450 DEG C of sintering temperature, roasted
The h of burning time 4, obtains oxidized catalyst.Compressing tablet, sieving are carried out to calcined catalyst, 20-40 mesh particle is chosen and is loaded reaction
Device.In 4 MPa, 360 DEG C, 2 h-1, reversion in device is carried out to catalyst under conditions of G/L=500, gained catalyst compares table
Area is 102 m2/ g, the cm of pore volume 0.163/ g, the nm of average pore size 6.3.
Embodiment 4
According to Ni:Mo:W=3:1:1 metal molar proportioning weighs the g of Nickel dichloride hexahydrate 14.280, the g of ammonium heptamolybdate 5.071,
The g of ammonium metatungstate 3.531.Mo, W compound are poured into the there-necked flask of 500 ml capacity, with the deionized water of 300 ml 50
It is completely dissolved at DEG C, is obtained solution A.The pH=9 of solution A is adjusted as precipitating reagent with ammoniacal liquor, heating water bath solution A temperature is extremely
90 ℃.Nickel dichloride hexahydrate is poured into beaker with 20 ml deionized water dissolvings, solution B is obtained.It is under equality of temperature that solution B is slow
In instillation solution A, it is seen that there is precipitation to increasingly generate.After after completion of dropping, the h of agitating solution 5 at 90 DEG C fills active component
Divide compound.The g of PEG 1.812 g, SB powder 3.624 is separately added into solution in whipping process, it is to be mixed finish after, stand and suspend
Liquid is carrying out burin-in process, the h of ageing time 2 to it.Suction filtration suspension after aging end, washs filter cake.Filter cake is placed in infrared
In drying box, 12 h are dried at 110 DEG C, catalyst precursor is obtained.Presoma is calcined, 450 DEG C of sintering temperature,
The h of roasting time 4, obtains oxidized catalyst.Compressing tablet, sieving are carried out to calcined catalyst, 20-40 mesh particle is chosen and is loaded anti-
Answer device.In 4 MPa, 360 DEG C, 2 h-1, reversion in device, gained catalyst ratio are carried out to catalyst under conditions of G/L=500
Surface area is 93 m2/ g, the cm of pore volume 0.163/ g, the nm of average pore size 5.8.
Embodiment 5
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs the g of nickel acetate tetrahydrate 9.954, the g of ammonium heptamolybdate 5.071, partially
The g of ammonium tungstate 3.531.Mo, W compound are poured into the there-necked flask of 500 ml capacity, with the deionized water of 300 ml at 50 DEG C
It is lower to be completely dissolved, obtain solution A.The pH=9 of solution A, heating water bath solution A temperature to 90 are adjusted as precipitating reagent with ammoniacal liquor
℃.Nickel acetate tetrahydrate is poured into beaker to be dissolved with appropriate amount of deionized water, solution B is obtained.Solution B is changed into slow instillation under equality of temperature
In solution A, it is seen that there is precipitation to increasingly generate.The g of PEG 1.856 g, SB powder 3.711 is separately added into solution in whipping process,
After after after completion of dropping, the h of agitating solution 5 at 90 DEG C makes active component fully be combined.Stirring finishes rear suction filtration suspension,
Washing filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 110 DEG C, catalyst precursor is obtained.To presoma
It is calcined, 450 DEG C of sintering temperature, the h of roasting time 4 obtains oxidized catalyst.Compressing tablet, mistake are carried out to calcined catalyst
Sieve, chooses 20-40 mesh particle and loads reactor.In 4 MPa, 360 DEG C, 2 h-1, catalyst is carried out under conditions of G/L=500
Reversion in device, gained specific surface area of catalyst is 72 m2/ g, the cm of pore volume 0.133/ g, the nm of average pore size 5.2.
Embodiment 6
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs the g of nickel acetate tetrahydrate 9.954 respectively, ammonium heptamolybdate 5.071
G, the g of ammonium metatungstate 3.531.Mo, W compound are poured into the there-necked flask of 500 ml capacity, with the deionized water of 300 ml 50
It is completely dissolved at DEG C.Selected precipitating reagent is sodium acid carbonate, and precipitating reagent regulation solution A to appropriate pH value range is
11.It is disposable addition that solution B adds the mode of solution A；It is disposable addition that PEG adds the mode of solution；SB powder adds molten
The mode of liquid is disposably added.The time of described hydrothermal aging is 6 h.Calcination process is carried out to catalyst precursor, is calcined
Temperature is 300 DEG C, and roasting time is 2h, and roasting obtains corresponding oxidized catalyst after terminating；Oxidized catalyst is carried out
Reversion in device, reduction pressure is 2 MPa, and temperature is 200 DEG C, and air speed is 1h-1, hydrogen to oil volume ratio is 200, and the recovery time is
4 h, reduction process obtains corresponding sulphided state catalyst after terminating.The molecular weight of described PEG is 100-10000.Described
The addition of SB powder accounts for the 10% of catalyst gross mass.Other steps are with embodiment 1.
Embodiment 7
According to Ni:Mo:W=3:1:1 metal molar proportioning weighs the g of nickel acetate tetrahydrate 14.931 respectively, ammonium heptamolybdate
5.071 g, the g of ammonium metatungstate 3.531.Mo, W compound are poured into the there-necked flask of 500 ml capacity, with the deionization of 300 ml
Water is completely dissolved at 50 DEG C.Selected precipitating reagent is sodium carbonate, and precipitating reagent regulation solution A to appropriate pH value is
8.Solution B adds the mode of solution A to be added dropwise over using equality of temperature；PEG adds the mode of solution to be slowly added into using equality of temperature；
SB powder adds the mode of solution to be slowly added into using equality of temperature.The time of described hydrothermal aging is 10 h.To complex catalyst precursor
Body carries out calcination process, and sintering temperature is 500 DEG C, and roasting time is 6 h, and roasting obtains corresponding oxidation state catalysis after terminating
Agent；Reversion in device is carried out to oxidized catalyst, reduction pressure is 4 MPa, and temperature is 400 DEG C, and air speed is 4 h-1, hydrogen
Oil volume ratio is 700, and the recovery time is 24 h, and reduction process obtains corresponding sulphided state catalyst after terminating.Described PEG's
Molecular weight is 100-20000.The addition of described SB powder accounts for the 30% of catalyst gross mass.Other steps are with embodiment 1.
The evaluation method of catalyst of the present invention is：
The activity rating of catalyst is carried out on the miniature hydrogenation reaction device of 10 ml high pressures.It is that Dalian west is catalyzed very much to evaluate raw material
Cracked diesel oil, raw material is pumped into using gear pump, and after cold high score and low pressure separator gas-liquid separation, product liquid is accessed and adopted product
Collection tank.After pre-vulcanization process terminates, temperature is reduced to 280 DEG C, pump into evaluation raw material.The h of stable reaction 6 is followed by sample, sample
Every 3 h collections are once.The Activity evaluation of the catalyst of several addition different molecular weight PEG is as shown in table 1.
Table 1 adds the heap density and desulfurization degree of the Ni-Mo-W unsupported catalysts of PEG and SB powder
Note：1-9# samples add different molecular weight PEG in representing Ni-Mo-W respectively
From table 1, it is apparent that PEG good peptizaiton and pore-creating performance have been affirmed, the peptizaiton for PEG
Should be understood in terms of two, be on the one hand the ability separated during it rolls into a ball Ni-Mo-W catalyst granules from big grain, separately
One side is the ability that it keeps this " separation " in whole course of reaction, and the PEG these two aspects abilities of different molecular weight
There were significant differences.When molecular weight gradually increases, the size increase of chain PEG, it is impossible to enter in Ni-Mo-W activearms gradation group
Portion, peptizaiton will necessarily decrease.Molecular weight continues to increase, and the steric hindrance of PEG also accordingly increases, now its dispersiveness
The dispersion between being rolled into a ball to catalyst pellets is shown as, dispersibility is strengthened once again, this also explains addition different molecular weight PEG
First increase specific surface area of catalyst the special trend for reducing again and increasing.From the point of view of dispersion stabilization angle, due to reaction
Carry out at a higher temperature, the PEG strands of macromolecule will necessarily produce certain fracture, its stability to temperature compared with
Difference, the PEG of small-molecular-weight is relatively low due to steric hindrance, compared to big component PEG, it is easier to be desorbed from Ni-Mo-W catalyst.
But for the preparation of unsupported catalyst, there is the PEG of optimum weight, make the pore structure of catalyst and desulfurization performance
Improve the most obvious.
The above implementation method is only several in many implementation methods of the invention, but protection scope of the present invention is not
It is confined to this.Protection scope of the present invention is defined by the protection domain of claims, and any those skilled in the art of the present technique exist
In the technical scope of present disclosure, the change or replacement that can be readily occurred in all are included within the scope of the present invention.
Claims (9)
1. a kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst, it is characterised in that system
Standby step includes：
(1) Mo, W ammonium salt of 0.02-0.1mol are weighed, 300 ml deionized water wiring solution-forming A is dissolved in, and adjust with precipitating reagent
Solution A is to appropriate pH value；
(2) water soluble nickel salt of 0.05-0.2mol is weighed for co-catalysis component raw material, is dissolved in 25 ml deionized water wiring solution-formings
B；
(3) solution A is added to mix solution B, it is seen that to have precipitation to generate, suspension of the stirring containing precipitation at 70-100 DEG C
3-8 h, add 0.02-0.1 mol PEG, 0.02-0.1 mol SB powder in whipping process, make active component compound complete, stir
Constant temperature stands solution after the completion of mixing, and burin-in process 4-18 h are carried out to it；
(4) ageing process terminates rear suction filtration suspension, and washs filter cake with deionized water, and filter cake is placed in into constant temperature infra-red drying
4-32 h are dried in case, catalyst precursor is obtained；
(5) reduction obtains final product the unsupported catalyst with good hydrodesulfurization activity in fired, device.
2. a kind of auxiliary agent PEG and SB powder that adds according to claim 1 is modified the system of Ni-based ternary unsupported catalyst
Preparation Method, it is characterised in that selected water soluble nickel salt can be Nickelous nitrate hexahydrate, nickel acetate tetrahydrate, six hydration chlorine
Change the one kind in nickel, nickel sulfate, two kinds of group vib metallic compounds are any two kinds in the ammonium salt of Mo, W or Cr.
3. a kind of auxiliary agent PEG and SB powder that adds according to claim 1 is modified the system of Ni-based ternary unsupported catalyst
Preparation Method, it is characterised in that the metal molar proportioning of co-catalysis component Ni and two kinds of group vib active components is water soluble nickel salt：
Ammonium heptamolybdate：Ammonium metatungstate=1: 1~4：1~4.
4. a kind of auxiliary agent PEG and SB powder that adds according to claim 1 is modified the system of Ni-based ternary unsupported catalyst
Preparation Method, it is characterised in that selected precipitating reagent is the one kind in ammoniacal liquor, sodium carbonate, sodium acid carbonate and NaOH.
5. a kind of auxiliary agent PEG and SB powder that adds according to claim 1 is modified the system of Ni-based ternary unsupported catalyst
Preparation Method, it is characterised in that it is to be added dropwise over or disposably add that solution B adds the mode of solution A, when being added dropwise over, uses
Equality of temperature or different temperature are added dropwise；It is to be slowly added into or disposably add that PEG adds the mode of solution, when being slowly added into, using equality of temperature or
Different temperature is poured into；It is to be slowly added into or disposably add that SB powder adds the mode of solution, when being slowly added into, is fallen using equality of temperature or different temperature
Enter.
6. a kind of auxiliary agent PEG and SB powder that adds according to claim 1 is modified the system of Ni-based ternary unsupported catalyst
Preparation Method, it is characterised in that the aging time described in step (3) is 6-10 h.
7. a kind of auxiliary agent PEG and SB powder that adds according to claim 1 is modified the system of Ni-based ternary unsupported catalyst
Preparation Method, it is characterised in that calcination process is carried out to catalyst precursor, sintering temperature is 300-500 DEG C, and roasting time is
2-6 h, roasting obtains corresponding oxidized catalyst after terminating；Reversion in device, reduction pressure are carried out to oxidized catalyst
Power is 2-4 MPa, and temperature is 200-400 DEG C, and air speed is 1-4 h-1, hydrogen to oil volume ratio is 200-700, and the recovery time is 4-24
H, reduction process obtains corresponding sulphided state catalyst after terminating.
8. a kind of auxiliary agent PEG and SB powder that adds according to claim 1 is modified the system of Ni-based ternary unsupported catalyst
Preparation Method, it is characterised in that the molecular weight of described PEG is 100-10000.
9. a kind of auxiliary agent PEG and SB powder that adds according to claim 1 is modified the system of Ni-based ternary unsupported catalyst
Preparation Method, it is characterised in that the addition of described SB powder accounts for the 10%-30% of catalyst gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710069386.5A CN106925288A (en) | 2017-02-08 | 2017-02-08 | A kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710069386.5A CN106925288A (en) | 2017-02-08 | 2017-02-08 | A kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106925288A true CN106925288A (en) | 2017-07-07 |
Family
ID=59422946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710069386.5A Pending CN106925288A (en) | 2017-02-08 | 2017-02-08 | A kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106925288A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950470A (en) * | 2022-06-30 | 2022-08-30 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application of nickel-based catalyst in selective hydrogenation of propyne and propadiene in propylene |
| CN115069263A (en) * | 2022-07-25 | 2022-09-20 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application thereof in butadiene selective hydrogenation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6783663B1 (en) * | 1997-07-15 | 2004-08-31 | Exxonmobil Research And Engineering Company | Hydrotreating using bulk multimetallic catalysts |
| EP1791639A1 (en) * | 2004-09-22 | 2007-06-06 | Exxonmobil Research And Engineering Company | BULK Ni-Mo-W CATALYSTS MADE FROM PRECURSORS CONTAINING AN ORGANIC AGENT |
| CN101306374A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition, preparation method and use thereof |
| WO2015171277A1 (en) * | 2014-05-05 | 2015-11-12 | Exxonmobil Research And Engineering Company | Hydroprocessing catalysts and their production |
-
2017
- 2017-02-08 CN CN201710069386.5A patent/CN106925288A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6783663B1 (en) * | 1997-07-15 | 2004-08-31 | Exxonmobil Research And Engineering Company | Hydrotreating using bulk multimetallic catalysts |
| EP1791639A1 (en) * | 2004-09-22 | 2007-06-06 | Exxonmobil Research And Engineering Company | BULK Ni-Mo-W CATALYSTS MADE FROM PRECURSORS CONTAINING AN ORGANIC AGENT |
| CN101306374A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition, preparation method and use thereof |
| WO2015171277A1 (en) * | 2014-05-05 | 2015-11-12 | Exxonmobil Research And Engineering Company | Hydroprocessing catalysts and their production |
Non-Patent Citations (4)
| Title |
|---|
| 任丽丽: ""共沉淀法制备非负载型Ni-Mo-W催化剂及性能研究"", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
| 张俊萍: ""非负载型双金属催化剂的制备、表征与加氢性能评价"", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
| 曾鹤 等: ""老化成胶和磷改性对非负载型催化剂结构和性能的影响"", 《石油化工》 * |
| 柴磊昌 等: ""沉淀法制备体相Ni-Mo型催化剂过程中添加PEG的作用研究"", 《应用化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950470A (en) * | 2022-06-30 | 2022-08-30 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application of nickel-based catalyst in selective hydrogenation of propyne and propadiene in propylene |
| CN114950470B (en) * | 2022-06-30 | 2023-07-25 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application thereof in selective hydrogenation of propyne and propadiene in propylene |
| CN115069263A (en) * | 2022-07-25 | 2022-09-20 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application thereof in butadiene selective hydrogenation |
| CN115069263B (en) * | 2022-07-25 | 2023-07-25 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application thereof in butadiene selective hydrogenation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102451765B (en) | Preparation method for composite oxide carrier | |
| CN104096563B (en) | Fe-series catalyst and preparation method thereof | |
| CN101298046B (en) | Iron catalyst containing titanium deposition for catalyzing Fischer-Tropsch synthesis reaction and method for producing the same | |
| CN102847541B (en) | Coal tar hydrodemetalization catalyst and preparation method thereof | |
| CN105457648B (en) | Iron molybdenum formaldehyde synthetic catalyst and preparation method thereof | |
| CN103212432B (en) | Catalyst for hydro-denitrification of inferior heavy distillate oil and preparation method and application of catalyst | |
| CN109912372A (en) | Synthesis gas methanation catalyst and its preparation method | |
| CN106925288A (en) | A kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst | |
| CN104549490A (en) | Method for recycling and reusing waste hydrocracking catalyst through ultrasonication | |
| CN107565124A (en) | A kind of precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof | |
| CN106784783B (en) | The method of synthesizing lithium ion battery nickel cobalt manganese anode material | |
| CN107442166A (en) | Hydrogenation catalyst suitable for producing biodiesel and its preparation method and application | |
| CN104888797A (en) | Iron-based catalyst and preparation method thereof | |
| CN109395770A (en) | A kind of iron-based hydrogenation catalyst and preparation method thereof | |
| CN107321354B (en) | A kind of highly selective carbon dioxide methanation catalyst of high temperature and preparation method thereof | |
| CN101966454B (en) | Catalyst for use in preparation of hydrogen peroxide by anthraquinone method and preparation method thereof | |
| CN113893840A (en) | Composite photocatalyst, preparation method and application in dye wastewater | |
| CN108311134A (en) | Diesel vehicle/steamer tail gas SCR denitration titanium tungsten silicon composite powder and preparation method | |
| CN107362825A (en) | Exempt to be calcined hydrogenation catalyst and its preparation method and application | |
| CN110732328B (en) | Multi-core shell structure nickel-based catalyst for carbon dioxide reforming reaction and preparation method and application thereof | |
| CN106902836A (en) | A kind of preparation method of addition SDBS and diatomite modified ternary metal bulk phase catalyst | |
| CN106824216A (en) | A kind of preparation method for adding additive modification ternary metal bulk phase catalyst | |
| CN108630953A (en) | A kind of difunctional oxygen precipitation-oxygen reduction non-noble metal catalyst and preparation method thereof | |
| CN107096539A (en) | A kind of low carbon alcohol by synthetic gas catalyst and preparation method thereof, application | |
| CN106582757B (en) | Dehydroepiandros-sterone adds hydrogen palladium/calcium carbonate catalyst preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170707 |