CN106902836A - A kind of preparation method of addition SDBS and diatomite modified ternary metal bulk phase catalyst - Google Patents
A kind of preparation method of addition SDBS and diatomite modified ternary metal bulk phase catalyst Download PDFInfo
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- CN106902836A CN106902836A CN201710069300.9A CN201710069300A CN106902836A CN 106902836 A CN106902836 A CN 106902836A CN 201710069300 A CN201710069300 A CN 201710069300A CN 106902836 A CN106902836 A CN 106902836A
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- catalyst
- sdbs
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- bulk phase
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000032683 aging Effects 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 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
- 239000000725 suspension Substances 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000007603 infrared drying Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000005245 sintering 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
- 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
- 238000003756 stirring Methods 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
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 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
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 235000016768 molybdenum Nutrition 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
- 230000023556 desulfurization Effects 0.000 abstract description 5
- 239000002270 dispersing agent Substances 0.000 abstract 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 16
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction 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
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003657 tungsten Chemical class 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- 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
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of addition SDBS and the preparation method of diatomite modified ternary metal bulk phase catalyst, two kinds of different auxiliary agents are introduced i.e. during coprecipitation prepares unsupported catalyst, active component, auxiliary agent are combined, i.e., SDBS and diatomite are 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, modified catalyst is obtained deep hydrodesulfurizationof performance and is greatly improved the strict demand for meeting GB after the hydrogenation reaction to diesel deep desulfurization.
Description
Technical field
The present invention relates to field of catalyst preparation, specifically a kind of addition SDBS and diatomite modified ternary metal body phase are urged
The preparation method of agent.
Background technology
Because traditional loaded catalyst is due to having stronger interaction between active component and carrier, and loaded
Active metallic content it is limited, requirement now for desulfurizing oil depth cannot have been met, therefore to unsupported catalyst
Preparation with study it is imperative.A kind of preparation method of loaded catalyst is described in United States Patent (USP) US 6620313, i.e.,
The suspension of 90 DEG C of molybdenum salt, tungsten salt mixed liquor and insoluble nickel salt is respectively configured, and 20 h are mixed at 90 DEG C, passed through
Filter, washing, dry, shaping, roasting finally give oxidation state unsupported catalyst, and there is obtained catalyst preferable hole to tie
Structure and specific surface area.A kind of preparation method of loaded catalyst, the load for being used are described in European patent EP 0469675
Body is the mixture of Woelm Alumina, porous molecular screen and amorphous aluminum silicate, and gained catalyst pores gap structure is more flourishing.
Chinese invention patent CN 101255356 describes a kind of non-loading type catalysis for intermediate base distillate oil deep hydrofinishing
The preparation method of agent, is reacted by urea melting, obtains a kind of catalyst itself with nano pore and high specific surface area
Particulate matter, the catalyst has abundant catalytic hydrogenation activity position.
But the above-mentioned catalyst developed is respectively provided with some shortcomings of itself, such as catalytic mechanical intensity is poor, metal is lived
Property center is excessively intensive, industrializeding catalyst that is preparing is on the high side etc..Therefore, it is badly in need of a kind of new preparation method of exploitation, it is right
The syntheti c route of existing unsupported catalyst is improved, to further improving the Hydrogenation of catalyst and can be used for work
Industry metaplasia is produced.
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 preparation method of addition SDBS and diatomite modified ternary metal bulk phase catalyst, 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 to appropriate pH value to 8-10 in the range of；
(2) water soluble nickel salt of 0.05-0.2mol is weighed for co-catalysis component raw material, is dissolved in 20ml 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 0.02-0.15mol SDBS and 0.02-0.15mol diatomite in whipping process, make active component compound complete,
Constant temperature stands solution after the completion of stirring, 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 source can be Nickelous nitrate hexahydrate, nickel acetate tetrahydrate, nickel chloride, nickel sulfate
In one kind, 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 SDBS 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 diatomite 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 8-12h.
Wherein, calcination process is carried out to catalyst precursor, sintering temperature is 300-550 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 SDBS is 348.48, and HLB value is 10.638.
Wherein, described diatomaceous addition accounts for the 15%-35% 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 80-150 m2/ g, pore volume is 0.17-
0.22cm3/ g, average pore size is 5.9-6.8 nm.The catalyst particle size is fine, and rate of metal is high, adds with preferable
Hydrogen desulphurization reaction activity.
(2) preparation process of catalyst is simple, easy to operate, and preparation condition is gentle, beneficial to industrialized production and application.
(3) 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.
(4) 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%.
Brief description of the drawings
Fig. 1 is the shape appearance figure 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.By the g of SDBS 1.856 in whipping process, the g of diatomite 3.711 is separately added into solution,
It is to be mixed finish after, stand suspension carrying out hydrothermal aging treatment, the h of ageing time 2 to it.Suction filtration suspends after aging end
Liquid, washs filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 120 DEG C, catalyst precursor is obtained.To forerunner
Body is calcined, 450 DEG C of sintering temperature, and the h of roasting time 4 obtains oxidized catalyst.Calcined catalyst is carried out compressing tablet,
Sieving, chooses 20-40 mesh particle and loads reactor.In 4 MPa, 350 DEG C, 2 h-1, catalyst is entered under conditions of G/L=500
Reversion in row device, gained specific surface area of catalyst is 79 m2/ g, the cm of pore volume 0.143/ g, the nm of average pore size 5.5.
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.By the g of SDBS 2.023 in whipping process, the g of diatomite 4.047 is separately added into solution, it is to be mixed finish after, stand
Suspension is carrying out hydrothermal aging treatment, the h of ageing time 2 to it.Suction filtration suspension after aging end, washs filter cake.By filter cake
It is placed in infrared drying oven, 12 h is dried at 110 DEG C, catalyst precursor is obtained.Presoma is calcined, roasting temperature
450 DEG C of degree, the h of roasting time 4 obtains oxidized catalyst.Compressing tablet, sieving are carried out to calcined catalyst, 20-40 mesh is chosen
Grain loads reactor.In 4 MPa, 360 DEG C, 2 h-1, reversion in device, gained are carried out to catalyst under conditions of G/L=500
Specific surface area of catalyst is 86 m2/ g, the cm of pore volume 0.153/ g, the nm of average pore size 5.8.
Fig. 1 is the shape appearance figure of the present embodiment gained catalyst.
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 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 dichloride hexahydrate is poured into beaker with 20 ml deionized water dissolvings, solution B is obtained.Solution B is changed into slow drop 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.By the g of SDBS 1.812 in whipping process, the g of diatomite 3.624 is separately added into solution, it is to be mixed finish after, stand outstanding
Supernatant 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 put
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 particles are chosen
Load reactor.In 4 MPa, 360 DEG C, 2 h-1, reversion in device is carried out to catalyst under conditions of G/L=500, gained is urged
Agent specific surface area is 95 m2/ g, the cm of pore volume 0.153/ g, the nm of average pore size 6.0.
Embodiment 4
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs the g of Nickel dichloride hexahydrate 14.520, 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.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.By the g of SDBS 1.812 in whipping process, the g of diatomite 3.624 is separately added into solution, it is to be mixed finish after, stand
Suspension is carrying out hydrothermal aging treatment, the h of ageing time 4 to it.Suction filtration suspension after aging end, washs filter cake.By filter cake
It is placed in infrared drying oven, 12 h is dried at 110 DEG C, catalyst precursor is obtained.Presoma is calcined, roasting temperature
450 DEG C of degree, the h of roasting time 4 obtains oxidized catalyst.Compressing tablet, sieving are carried out to calcined catalyst, 20-40 mesh is chosen
Grain loads reactor.In 4 MPa, 360 DEG C, 2 h-1, reversion in device, gained are carried out to catalyst under conditions of G/L=500
Specific surface area of catalyst is 108 m2/ g, the cm of pore volume 0.173/ g, the nm of average pore size 6.4.
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.By the g of SDBS 1.856 in whipping process, the g of diatomite 3.711 is separately added into molten
Liquid, 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 and suspends
Liquid, washs filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 110 DEG C, catalyst precursor is obtained.To forerunner
Body is calcined, 450 DEG C of sintering temperature, and the h of roasting time 4 obtains oxidized catalyst.Calcined catalyst is carried out compressing tablet,
Sieving, chooses 20-40 mesh particle and loads reactor.In 4 MPa, 360 DEG C, 2 h-1, catalyst is entered under conditions of G/L=500
Reversion in row 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=1:1:1 metal molar proportioning weighs the g of nickel acetate tetrahydrate 4.977, 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.Selected precipitating reagent is sodium acid carbonate, and precipitating reagent adjusts solution A to appropriate pH value
Scope is 11.It is disposable addition that solution B adds the mode of solution A；It is disposable addition that SDBS adds the mode of solution；Diatom
Soil adds the mode of solution disposably to add.The time of described hydrothermal aging is 6 h.Catalyst precursor is carried out at roasting
Reason, sintering temperature is 300 DEG C, and roasting time is 2h, and roasting obtains corresponding oxidized catalyst after terminating；Oxidation state is catalyzed
Agent carries out reversion in device, and reduction pressure is 2 MPa, and temperature is 200 DEG C, and air speed is 1h-1, hydrogen to oil volume ratio is 200, reduction
Time is 4 h, and reduction process obtains corresponding sulphided state catalyst after terminating.Described SDBS is solid-state translucent crystal shape
State.Described diatomaceous addition accounts for the 10% of catalyst gross mass.
Embodiment 7
According to Ni:Mo:W=4:1:1 metal molar proportioning weighs the g of nickel acetate tetrahydrate 19.908, 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.Selected precipitating reagent is sodium carbonate, and precipitating reagent adjusts solution A to appropriate pH value
It is 8.Solution B adds the mode of solution A to be added dropwise over using equality of temperature；SDBS adds the mode of solution slowly to be added using equality of temperature
Enter；Diatomite adds the mode of solution to be slowly added into using equality of temperature.The time of described hydrothermal aging is 10 h.To catalyst
Presoma carries out calcination process, and sintering temperature is 500 DEG C, and roasting time is 6 h, and roasting obtains corresponding oxidation state after terminating
Catalyst；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 to oil volume ratio is 700, and the recovery time is 24 h, and reduction process obtains corresponding sulphided state catalyst after terminating.Described
SDBS.Described diatomaceous addition accounts for the 30% of catalyst gross mass.
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 20 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 SDBS and diatomaceous Ni-Mo-W unsupported catalysts
Note：1-9# samples represent SDBS in Ni-Mo-W respectively：The different mol ratio value of diatomaceous addition
From table 1, it is apparent that addition auxiliary agent SDBS rear catalyst heaps density substantially diminishes and desulfurization degree is obviously improved, explanation
SDBS is suitable to the preparation of unsupported catalyst.SDBS can make particle concentration be unlikely to excessively dispersion into porous cluster, urge
Catalyst particles are more loose porous, embody less heap density, and significantly increase its specific surface area, catalyst HDS activity
Significantly improve.
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. the preparation method of a kind of addition SDBS and diatomite modified ternary metal bulk phase catalyst, it is characterised in that prepare step
Suddenly include：
(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 to appropriate pH value to 8-10 in the range of；
(2) water soluble nickel salt of 0.05-0.2mol is weighed for co-catalysis component raw material, is dissolved in 20ml 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 0.02-0.15mol SDBS and 0.02-0.15mol diatomite in whipping process, make active component compound complete,
Constant temperature stands solution after the completion of stirring, 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. the preparation side of a kind of addition SDBS according to claim 1 and diatomite modified ternary metal bulk phase catalyst
Method, it is characterised in that selected water-soluble nickel source can be Nickelous nitrate hexahydrate, nickel acetate tetrahydrate, nickel chloride, nickel sulfate
In one kind, two kinds of group vib metallic compounds are any two kinds in the ammonium salt of Mo, W or Cr.
3. the preparation side of a kind of addition SDBS according to claim 1 and diatomite modified ternary metal bulk phase catalyst
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：Seven molybdenums
Sour ammonium：Ammonium metatungstate=1: 1~4：1~4.
4. the preparation side of a kind of addition SDBS according to claim 1 and diatomite modified ternary metal bulk phase catalyst
Method, it is characterised in that selected precipitating reagent is the one kind in ammoniacal liquor, sodium carbonate, sodium acid carbonate and NaOH.
5. the preparation side of a kind of addition SDBS according to claim 1 and diatomite modified ternary metal bulk phase catalyst
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, using equality of temperature
Or different temperature is added dropwise；It is to be slowly added into or disposably add that SDBS adds the mode of solution, when being slowly added into, using equality of temperature or different temperature
Pour into；It is to be slowly added into or disposably add that diatomite adds the mode of solution, when being slowly added into, is fallen using equality of temperature or different temperature
Enter.
6. the preparation side of a kind of addition SDBS according to claim 1 and diatomite modified ternary metal bulk phase catalyst
Method, it is characterised in that the aging time described in step (3) is 8-12h.
7. the preparation side of a kind of addition SDBS according to claim 1 and diatomite modified ternary metal bulk phase catalyst
Method, it is characterised in that calcination process is carried out to catalyst precursor, sintering temperature is 300-550 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, also
Former process obtains corresponding sulphided state catalyst after terminating.
8. the preparation side of a kind of addition SDBS according to claim 1 and diatomite modified ternary metal bulk phase catalyst
Method, it is characterised in that the molecular weight of described SDBS is 348.48, and HLB value is 10.638.
9. the preparation side of a kind of addition SDBS according to claim 1 and diatomite modified ternary metal bulk phase catalyst
Method, it is characterised in that described diatomaceous addition accounts for the 15%-35% of catalyst gross mass.
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