CN106944089A - A kind of preparation method of the active sulphided state unsupported catalysts of high HDS - Google Patents
A kind of preparation method of the active sulphided state unsupported catalysts of high HDS Download PDFInfo
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- CN106944089A CN106944089A CN201710069186.XA CN201710069186A CN106944089A CN 106944089 A CN106944089 A CN 106944089A CN 201710069186 A CN201710069186 A CN 201710069186A CN 106944089 A CN106944089 A CN 106944089A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 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 12
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 16
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 235000007926 Craterellus fallax Nutrition 0.000 abstract 1
- 240000007175 Datura inoxia Species 0.000 abstract 1
- 239000008186 active pharmaceutical agent Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008236 heating water Substances 0.000 description 5
- 238000007603 infrared drying Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 244000275012 Sesbania cannabina Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 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
- -1 aluminum silicate Compound Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 125000000101 thioether group Chemical group 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
- B01J35/61—Surface area
- B01J35/615—100-500 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
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- 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
The invention discloses a kind of preparation method of the sulphided state unsupported catalyst with depth H DS activity.This method prepares a kind of good catalyst particles of flourishing, the active phase morphology of pore structure using transition metal Ni, Mo, W as active metal raw material by hydrothermal synthesis method.It is characterized in by preferred pre-vulcanization process to make catalyst vulcanization reduction effect during reversion in catalyst device good there is provided the desulphurizing activated position of more horn of plenty that the present invention is most prominent.Just because of this, the unsupported catalyst for preparing the present invention has the HDS activity higher compared to traditional supported catalysts.Meanwhile, simple to operate, mild condition of the invention, cost and energy consumption are relatively low, are adapted to mass industrial production.
Description
Technical field
The invention belongs to the hydrogenation catalyst field in Industrial Catalysis, more particularly to a kind of active sulphided states of high HDS are unsupported
The preparation method of type catalyst.
Background technology
With developing rapidly for industrial economy, the world is growing day by day to the demand of various oil products instantly, and this makes environmental problem
Puzzlement to people is more serious.With taking place frequently for haze weather and acid rain event, the environmental consciousness of people gradually strengthens, accordingly
Environmental regulation it is more and more harsh.At the same time, the crude oil of domestic production heaviness increasingly, and the sulfur content of imported crude oil is continuous
Rapid decrease trend is presented in increase, light crude oil resource, and such contradiction makes oil quality upgrading turn into what masses gave more sustained attention
Focus.European derv fuel standard is in world lead level, and most countries have been enter into the diesel oil ultra-clean stage, that is, require car
It is not more than 10 μ g/g with diesel oil sulfur content.China first carries out in urban rate on July 1st, 2015 and identical requires the row of state V
Put standard.At hand, the deep desulfuration of low grade oilses has been trend of the times for the implementation of the standard in China.
In numerous desulfurization methods of oil product, hydrofinishing is the effective means for realizing diesel deep desulfurization, is urged accordingly
The history of the application of agent in the industry existing decades.Generally speaking, it is still in the majority with the application to loaded catalyst at present.
Loaded catalyst is often prepared from infusion process, i.e., active component is carried on into γ-Al by impregnating2O3Or molecular sieve etc. is carried
On body, then active component good dispersion, the gentle Hydrobon catalyst of catalytic activity is made in the step such as fired, shaping.It is negative
The catalytic activity of supported catalyst is continued to optimize with the progress of technology of preparing, is described in European patent EP 0469675 a kind of negative
The preparation method of supported catalyst, the carrier used is the mixed of Woelm Alumina, porous molecular screen and amorphous aluminum silicate
Compound, gained catalyst pores gap structure is more flourishing；Chinese invention patent CN 1769376A disclose a kind of Acidic organic matter and changed
The method of property carrier, reduces the interaction between active component and carrier, significantly improves catalyst activity.But due to load
Interaction between the active component and carrier of type catalyst can not be completely eliminated, and the catalytic activity of loaded catalyst is limited
System, will reach that ultra-deep desulfurization generally requires more stringent process conditions and bigger energy consumption, therefore some new depth add
The technology of preparing of hydrogen catalyst is arisen at the historic moment.
Corresponding with loaded catalyst, unsupported catalyst becomes without using carrier, the HDS activity of its superelevation
The study hotspot of association area in recent years.Wherein, a kind of ternary metal non-loading type is disclosed in United States Patent (USP) US6299760B1
The preparation method of catalyst, it is to avoid the interaction between active component and carrier, gained catalyst has a microstructure, HDS
Activity is 2 times of conventional supported catalyst.Ni- is prepared using sol-gal process in Chinese invention patent CN 104785274A
Mo unsupported catalysts, its specific method is that soluble activating raw metal is dissolved in into ethanol water, and regulation solution is to suitable
Work as pH value, gel is formed it into by stirring, it is fired and produce bimetallic unsupported catalyst with sesbania powder kneading and compacting.
This method introduces expanding agent in catalyst preparation process, so that unsupported catalyst has suitable specific surface area and hole
Appearance, aperture, it is highly beneficial to improving its hydrogenation activity.Unsupported catalyst is because without using carrier, it is to avoid active component with
Interaction between carrier, but its intensive active component makes its metal dispersion and mechanical strength poor.
Existing technology of preparing is more to be conceived to the space development degree and heat endurance for improving unsupported catalyst,
Careful research is lacked to the process conditions in catalyst preparation and application process.In the reversion process of unsupported catalyst
In, preferred presulfurization condition, which forms the pore structure of prosperity, good active phase morphology pain to catalyst, has that very
Favorably.Therefore, a kind of preparation method ten of the good unsupported catalyst of abundant, the active phase morphology of reversion degree is developed
Divide necessity.
The content of the invention
It is an object of the invention to avoid in the prior art, unsupported catalyst reversion low degree, activity are mutually sparse
And the not good enough shortcoming of pattern, its hydrogenation reaction activity is effectively improved, use cost is reduced, the catalyst can be widely applied to poor quality
The hydrofinishing of diesel oil.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the active sulphided state unsupported catalysts of high HDS, comprises the following steps：
(1) 0.02-0.1mol Mo, W ammonium salt is weighed, 300 ml deionized water wiring solution-forming A are dissolved in, and adjust molten with precipitating reagent
Liquid A is to appropriate pH value；
(2) water soluble nickel salt for weighing 0.05-0.2mol is co-catalysis component raw material, is dissolved in 20 ml deionized water wiring solution-formings
B；
(3) solution B is added into solution A to being thoroughly mixed, it is seen that there is precipitation to generate, stirred after solution B is added dropwise to complete at 90 DEG C
The suspension containing precipitation is mixed, makes tentatively to be combined between active component.
(4) after 1-6 h, mixed liquor is poured into 2 L hydrothermal reaction kettles, reaction is stood in electric drying oven with forced convection；
(5) stand after reaction terminates and pour out suspension, through suction filtration, washing, dry obtained catalyst precursor；
(6) calcined catalyst presoma, obtains ternary metal oxidized catalyst, and compressing tablet, sieving are carried out to it, 20-40 mesh is selected
Grain is filled to fixed-bed micro-reactor, and sulphided state catalyst is obtained through presulfurization.
Wherein, selected Mo, W ammonium salt is respectively ammonium heptamolybdate, ammonium metatungstate.
Wherein, selected water-soluble nickel source is Nickelous nitrate hexahydrate.
Wherein, in presoma preparatory phase, selected precipitating reagent can be ammoniacal liquor, sodium carbonate, sodium acid carbonate and hydrogen
Sodium oxide molybdena, the pH value of solution A is 8-11 after being set up through precipitating reagent.
Wherein, calcination process is carried out to catalyst precursor, sintering temperature is 300-500 DEG C, and roasting time is 2-8 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 200-700：1, the recovery time is 4-24 h, reduction
Process obtains corresponding sulphided state catalyst after terminating.
Compared with existing unsupported catalyst technology of preparing, there is advantages below than the present invention：
(1) compared to existing unsupported catalyst technology of preparing, the significant technical characteristic of the present invention is in sulphided state catalysis
Preferred reversion technology is employed in agent preparation process, the specific surface area of the Ni base unsupported catalysts of preparation is 80-
120 m2/ g, pore volume is 0.13-0.17 cm3/ g, average pore size is 5.4-6.7 nm.The vulcanization of prepared unsupported catalyst
Reducing degree and sulphur atom utilization rate are higher, and pore structure is more flourishing, and active phase morphology is very good, catalyst HDS
Activity is significantly improved.
(2) present invention is simple to operate, and preparation condition is gentle, suitable for batch production and and industrial applications.
Brief description of the drawings
Fig. 1 is the SEM electron microscopes of the prepared catalyst of the embodiment of the present invention 3.
Embodiment
The present invention is described in further details with reference to embodiment, but protection scope of the present invention is not by embodiment institute
Limit.
Embodiment 1
Weigh the g of Nickelous nitrate hexahydrate 23.264, the g of ammonium heptamolybdate 10.142, the g of ammonium metatungstate 7.062.By ammonium heptamolybdate, inclined tungsten
Sour ammonium is poured into the there-necked flask of 500 ml capacity, is completely dissolved with 300 ml deionized water at 50 DEG C, obtains solution
A.The pH=9 that precipitating reagent adjusts solution A is added, heating water bath solution A temperature is to 90 DEG C.By Nickelous nitrate hexahydrate pour into beaker with
20 ml deionized water dissolvings, obtain solution B.Solution B is slowly dropped into solution A under equality of temperature, it is seen that there is precipitation gradually to give birth to
Into.After after completion of dropping, the original metal molar concentration of suspension is 0.5 mol/L.Make activity under 90 DEG C of hydrothermal condition
Tentatively it is combined between component, suspension is poured into 2 L hydrothermal reaction kettles after 1 h.The temperature for setting electric drying oven with forced convection is 150
DEG C, reactor is statically placed in and wherein react 5 h.Reaction terminates rear natural cooling hydro-thermal kettle, afterwards pours out suspension, suction filtration,
Washing, obtains presoma filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 110 DEG C, catalyst precursor is made.
Presoma is calcined, 400 DEG C of sintering temperature, the h of roasting time 4 obtains oxidized catalyst.Calcined catalyst is carried out
Compressing tablet, sieving, in 4 MPa, 320 DEG C, 1 h-1, reversion in device is carried out to catalyst under conditions of G/L=500, gained is urged
Agent specific surface area is 91 m2/ g, the cm of pore volume 0.143/ g, the nm of average pore size 5.9.
Embodiment 2
Weigh the g of Nickelous nitrate hexahydrate 23.264, the g of ammonium heptamolybdate 10.142, the g of ammonium metatungstate 7.062.By ammonium heptamolybdate, inclined tungsten
Sour ammonium is poured into the there-necked flask of 500 ml capacity, is completely dissolved with 300 ml deionized water at 50 DEG C, obtains solution
A.The pH=9 that precipitating reagent adjusts solution A is added, heating water bath solution A temperature is to 90 DEG C.By Nickelous nitrate hexahydrate pour into beaker with
20 ml deionized water dissolvings, obtain solution B.Solution B is slowly dropped into solution A under equality of temperature, it is seen that there is precipitation gradually to give birth to
Into.After after completion of dropping, the original metal molar concentration of suspension is 0.5 mol/L.Make activity under 90 DEG C of hydrothermal condition
Tentatively it is combined between component, suspension is poured into 2 L hydrothermal reaction kettles after 1 h.The temperature for setting electric drying oven with forced convection is 150
DEG C, reactor is statically placed in and wherein react 5 h.Reaction terminates rear natural cooling hydro-thermal kettle, afterwards pours out suspension, suction filtration,
Washing, obtains presoma filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 110 DEG C, catalyst precursor is made.
Presoma is calcined, 400 DEG C of sintering temperature, the h of roasting time 4 obtains oxidized catalyst.Calcined catalyst is carried out
Compressing tablet, sieving, in 4 MPa, 340 DEG C, 1 h-1, reversion in device is carried out to catalyst under conditions of G/L=500, gained is urged
Agent specific surface area is 109 m2/ g, the cm of pore volume 0.163/ g, the nm of average pore size 6.5.
Embodiment 3
Weigh the g of Nickelous nitrate hexahydrate 23.264, the g of ammonium heptamolybdate 10.142, the g of ammonium metatungstate 7.062.By ammonium heptamolybdate, inclined tungsten
Sour ammonium is poured into the there-necked flask of 500 ml capacity, is completely dissolved with 300 ml deionized water at 50 DEG C, obtains solution
A.The pH=9 that precipitating reagent adjusts solution A is added, heating water bath solution A temperature is to 90 DEG C.By Nickelous nitrate hexahydrate pour into beaker with
20 ml deionized water dissolvings, obtain solution B.Solution B is slowly dropped into solution A under equality of temperature, it is seen that there is precipitation gradually to give birth to
Into.After after completion of dropping, the original metal molar concentration of suspension is 0.5 mol/L.Make activity under 90 DEG C of hydrothermal condition
Tentatively it is combined between component, suspension is poured into 2 L hydrothermal reaction kettles after 1 h.The temperature for setting electric drying oven with forced convection is 150
DEG C, reactor is statically placed in and wherein react 5 h.Reaction terminates rear natural cooling hydro-thermal kettle, afterwards pours out suspension, suction filtration,
Washing, obtains presoma filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 110 DEG C, catalyst precursor is made.
Presoma is calcined, 400 DEG C of sintering temperature, the h of roasting time 4 obtains oxidized catalyst.Calcined catalyst is carried out
Compressing tablet, sieving, in 4 MPa, 360 DEG C, 1 h-1, reversion in device is carried out to catalyst under conditions of G/L=500, gained is urged
Agent specific surface area is 118 m2/ g, the cm of pore volume 0.173/ g, the nm of average pore size 6.7.
Fig. 1 is the SEM electron microscopes of the present embodiment prepared catalyst, as the catalyst prepared by the figure can be seen that the present invention
With good active phase microscopic appearance.
Embodiment 4
This example illustrates the preparation method of comparative catalyst, and the pressure of reversion process is 2 in the catalyst preparation process
MPa。
Weigh the g of Nickelous nitrate hexahydrate 23.264, the g of ammonium heptamolybdate 10.142, the g of ammonium metatungstate 7.062.By ammonium heptamolybdate,
Ammonium metatungstate is poured into the there-necked flask of 500 ml capacity, is completely dissolved, obtained at 50 DEG C with 300 ml deionized water
Solution A.The pH=9 that precipitating reagent adjusts solution A is added, heating water bath solution A temperature is to 90 DEG C.Nickelous nitrate hexahydrate is poured into burning
Cup obtains solution B with 20 ml deionized water dissolvings.Solution B is slowly dropped into solution A under equality of temperature, it is seen that have precipitation gradually
Generation.After after completion of dropping, the original metal molar concentration of suspension is 0.5 mol/L.Make work under 90 DEG C of hydrothermal condition
Property component between tentatively be combined, suspension is poured into 2 L hydrothermal reaction kettles after 1 h.The temperature for setting electric drying oven with forced convection is 150
DEG C, reactor is statically placed in and wherein react 5 h.Reaction terminates rear natural cooling hydro-thermal kettle, afterwards pours out suspension, suction filtration,
Washing, obtains presoma filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 110 DEG C, catalyst precursor is made.
Presoma is calcined, 400 DEG C of sintering temperature, the h of roasting time 4 obtains oxidized catalyst.Calcined catalyst is carried out
Compressing tablet, sieving, in 2 MPa, 360 DEG C, 1 h-1, reversion in device is carried out to catalyst under conditions of G/L=500, gained is urged
Agent specific surface area is 80 m2/ g, the cm of pore volume 0.133/ g, the nm of average pore size 5.5.
Embodiment 5
This example illustrates the preparation method of comparative catalyst, and the air speed of reversion process is 2 h in the catalyst preparation process-1。
Weigh the g of Nickelous nitrate hexahydrate 23.264, the g of ammonium heptamolybdate 10.142, the g of ammonium metatungstate 7.062.By ammonium heptamolybdate,
Ammonium metatungstate is poured into the there-necked flask of 500 ml capacity, is completely dissolved, obtained at 50 DEG C with 300 ml deionized water
Solution A.The pH=9 that precipitating reagent adjusts solution A is added, heating water bath solution A temperature is to 90 DEG C.Nickelous nitrate hexahydrate is poured into burning
Cup obtains solution B with 20 ml deionized water dissolvings.Solution B is slowly dropped into solution A under equality of temperature, it is seen that have precipitation gradually
Generation.After after completion of dropping, the original metal molar concentration of suspension is 0.5 mol/L.Make work under 90 DEG C of hydrothermal condition
Property component between tentatively be combined, suspension is poured into 2 L hydrothermal reaction kettles after 1 h.The temperature for setting electric drying oven with forced convection is 150
DEG C, reactor is statically placed in and wherein react 5 h.Reaction terminates rear natural cooling hydro-thermal kettle, afterwards pours out suspension, suction filtration,
Washing, obtains presoma filter cake.Filter cake is placed in infrared drying oven, 12 h are dried at 110 DEG C, catalyst precursor is made.
Presoma is calcined, 400 DEG C of sintering temperature, the h of roasting time 4 obtains oxidized catalyst.Calcined catalyst is carried out
Compressing tablet, sieving, 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 104 m2/ g, the cm of pore volume 0.153/ g, the nm of average pore size 6.3.
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 product is after cold high score and low pressure separator gas-liquid separation, and product liquid access is adopted
Collect tank.After pre-vulcanization process terminates, reduction temperature is pumped into evaluation raw material to 280 DEG C.The h of stable reaction 6 is followed by sample, and sample is every
3 h are gathered once.Sulfide content in raw material and product is determined using the ANTEK9000 type sulphur blood urea/nitrogen analyzer of ANTEK companies, adopted
With the Clarus500 types gas chromatograph and sulphur luminescence detector of PerkinElmer companies（SCD）Combination analysis oil product sulfide
Form.The Activity evaluation of several catalyst is as shown in table 1.
The catalyst activity evaluation result of the present invention of table 1
| Catalyst | F1 | F2 | F3 | F4 | F5 |
| HDS% | 97.5 | 98.2 | 98.9 | 96.7 | 98.0 |
F1-F5 is respectively numbering of the present invention by embodiment 1-5 prepared catalysts, and HDS% is the hydrodesulfurization rate of catalyst.
The above embodiment is only several in many embodiments 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 (6)
1. a kind of preparation method of the active sulphided state unsupported catalysts of high HDS, it is characterised in that comprise the following steps：
(1) 0.02-0.1mol Mo, W ammonium salt is weighed, 300 ml deionized water wiring solution-forming A are dissolved in, and adjust with precipitating reagent
Solution A is to appropriate pH value；
(2) water soluble nickel salt for weighing 0.05-0.2mol is co-catalysis component raw material, is dissolved in 20 ml deionized water wiring solution-formings
B；
(3) solution B is added into solution A to being thoroughly mixed, it is seen that there is precipitation to generate, stirred after solution B is added dropwise to complete at 90 DEG C
The suspension containing precipitation is mixed, makes tentatively to be combined between active component.
2. (4) after 1-6 h, mixed liquor is poured into 2 L hydrothermal reaction kettles, reaction is stood in electric drying oven with forced convection；
(5) stand after reaction terminates and pour out suspension, through suction filtration, washing, dry obtained catalyst precursor；
(6) calcined catalyst presoma, obtains ternary metal oxidized catalyst, and compressing tablet, sieving are carried out to it, 20-40 mesh is selected
Grain is filled to fixed-bed micro-reactor, and sulphided state catalyst is obtained through presulfurization.
3. a kind of preparation method of the active sulphided state unsupported catalysts of high HDS according to claim 1, its feature exists
In selected Mo, W ammonium salt is respectively ammonium heptamolybdate, ammonium metatungstate.
4. a kind of preparation method of the active sulphided state unsupported catalysts of high HDS according to claim 1, its feature exists
In selected water-soluble nickel source is Nickelous nitrate hexahydrate.
5. a kind of preparation method of the active sulphided state unsupported catalysts of high HDS according to claim 1, its feature exists
In in presoma preparatory phase, selected precipitating reagent can be ammoniacal liquor, sodium carbonate, sodium acid carbonate and NaOH, through heavy
The pH value of solution A is 8-11 after the agent setting of shallow lake.
6. a kind of preparation method of the active sulphided state unsupported catalysts of high HDS according to claim 1, its feature exists
In to catalyst precursor progress calcination process, sintering temperature is 300-500 DEG C, and roasting time is 2-8 h, after roasting terminates
Obtain corresponding oxidized catalyst；Reversion in device is carried out to oxidized catalyst, reduction pressure is 2-4 MPa, temperature
For 200-400 DEG C, air speed is 1-4 h-1, hydrogen to oil volume ratio is 200-700：1, the recovery time is 4-24 h, and reduction process terminates
After obtain corresponding sulphided state catalyst.
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| CN109289876A (en) * | 2018-11-23 | 2019-02-01 | 中国石油大学(北京) | A kind of deep desulfurization catalyst and its preparation method and application |
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