CN106268871A - A kind of load type Co MoS2/LDHS Hydrobon catalyst and application - Google Patents
A kind of load type Co MoS2/LDHS Hydrobon catalyst and application Download PDFInfo
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- CN106268871A CN106268871A CN201610559029.2A CN201610559029A CN106268871A CN 106268871 A CN106268871 A CN 106268871A CN 201610559029 A CN201610559029 A CN 201610559029A CN 106268871 A CN106268871 A CN 106268871A
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- catalyst
- mos
- ldhs
- houghite
- ionic liquid
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052961 molybdenite Inorganic materials 0.000 title claims description 48
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000295 fuel oil Substances 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- -1 1-methyl-3-carboxyethyl imidazoles Tetrafluoroborate Chemical class 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000002086 nanomaterial Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 238000002242 deionisation method Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 2
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000005486 sulfidation Methods 0.000 abstract description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 abstract 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003027 oil sand Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OACWYUMBVZPQQN-UHFFFAOYSA-N 3-(3-methyl-2h-imidazol-1-yl)propanoic acid Chemical class CN1CN(CCC(O)=O)C=C1 OACWYUMBVZPQQN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (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 hydrofinishing catalytic field, particularly relate to load type Co MoS prepared by a kind of ionic liquid2/ LDHS Hydrobon catalyst, gained composite is with cobalt molybdenum bisuphide and the structure of houghite and performance advantage, in synthetic system, eliminate the sulfidation of vulcanizing agent and molybdate precursor, directly from raw material control, it is aided with solvent effect, improves the dispersibility of nano molybdenum disulfide, catalyst has good thermostability, crushing resistance and heat stability.
Description
Technical field
The present invention relates to hydrofinishing field, particularly relate to a kind of load type Co-MoS using ionic liquid to prepare2/
LDHS Hydrobon catalyst and application thereof.
Background technology
In heavy oil (such as the reduced crude of crude oil, the decompression residuum of crude oil, heavy crude, oil-sand, synthetic heavy oil product etc.)
Containing impurity such as substantial amounts of heavy metal (such as nickel, vanadium), sulfur, nitrogen, and the content of resin and asphalt is higher, splits to meet catalysis
Change the requirement of charging, protect downstream catalyst, it is necessary to removed as much as possible by these impurity, and hydrotreating is that removing is above-mentioned miscellaneous
The optimum technique of matter.Heavy oil hydrogenating treatment catalyst divides and generally comprises protective agent, catalyst for demetalation, desulfurization by using function
Catalyst, reforming catalyst etc..The Main Function of reforming catalyst is exactly to remove to greatest extent through demetalization and desulfurizing agent
Sulfur, nitrogen and carbon residue etc. in material.Additionally, in heavy-oil hydrogenation processing procedure, owing to furol viscosity is high and impurity content is big, because of
The air speed of this heavy-oil hydrogenation processing procedure is the least, so the consumption of catalyst is relatively greatly increased than other oil refining process, and weight
Oil hydrogenating treatment catalyst is short for service life, and recyclability is poor, and the cost therefore reducing catalyst is particularly important.
Molybdenum bisuphide, as a kind of layered semiconductor material with class graphene-structured, nowadays has been obtained for people more
Get over and pay close attention to widely, and show good application prospect at microelectronic.But, molybdenum bisuphide not only has excellent
Different electric property, it has good catalysis activity equally.As a kind of traditional Hydrobon catalyst, molybdenum bisuphide exists
Industrial application has had many decades, and meanwhile, research in the last few years shows, molybdenum bisuphide tool same for Hydrogen evolving reaction
There is the catalysis activity of excellence, it is possible to for the acquisition of the hydrogen energy source of the feature of environmental protection.This makes it change neck at catalytic field and energy
Territory all has fabulous application potential.Houghite (writing a Chinese character in simplified form LDH) is a class two-dimensional nanometer anionic clay, and its composition formula can
It is expressed as [M1-x 2+Mx 3+(OH)2]x+(An-)x/n·mH2O, wherein M2+Refer to divalent metal, M3+Refer to trivalent metal cation,
X is M2+With M3+Mol ratio, A n-For interlayer can the anion of stable existence, there is hydrotalcite layered structure, because of its lamella element
Composition and charge density is adjustable, interlayer guest molecule, crystalline size are controlled, and the advantage such as bio-toxicity is low, urge organic
The numerous areas such as change, polymeric additive, biological medicine, environmental conservation present good application prospect.
Summary of the invention
For the demand of existing hydrodesulfurization technology, more and more severe for raw material, heavy oil, viscous crude, residual oil or oil-sand drip
The resource such as blue or green utilize expanding day, the Hydrobon catalyst for special oil product has stricter demand.
The present invention uses the method for ionic liquid to obtain MoS2Load hydrotalcite-like materials LDHS, further carried metal
Cobalt, obtains can be used in heavy-oil hydrogenation catalyst for refining.Described Co-MoS2In/LDHS, MoS2Surface at houghite carrier
Formed and close put monolayer.Overall based on catalyst, metal Co content is 5-15wt%, MoS2Content is 5-15wt%.
The preparation method of heavy-oil hydrogenation catalyst for refining provided by the present invention includes:
(1) preparation of nano molybdenum disulfide: add tetrathiomolybdate in solvent, ionic liquid stirs, and is subsequently adding
Appropriate reducing agent, stirs, and is configured to initial reaction mixture and is transferred in Autoclaves for synthesis；
(2) MoS2Load houghite: by ZnCl2、FeCl3And FeCl2Be dissolved into respectively in water, be configured to concentration be 1～
The solution of 2mol/L, by three kinds of solution mixing, keeps Zn2+: Fe2+: Fe3+Mol ratio be (2～4): (1～2): 1, at constant temperature
Instilling a certain amount of alkaline solution in 70～80 DEG C of water-baths, react 2～3h, aging 12～24h, formation has layer in this process
The houghite precipitation of shape structure, precipitate and separate, deionization is washed 2～3 times, calcines 1-5h at a temperature of 400～550 DEG C；
Houghite is dispersed to containing MoS2Synthesis reactor, add deionized water, hydro-thermal reaction 12h at keeping 150-200 DEG C, cold
But, centrifugation, washing, solid product, washing, it is dried, obtains nanometer MoS2/ LDHS composite nano materials.
(3) nanometer MoS2/ LDHS composite nano materials is immersed in 0.05-0.1mol/l cobalt nitrate solution, is sufficiently stirred for
Uniformly, standing 2-5 hour, aging 10-12 hour, filter, be dried, 400-500 DEG C of roasting 2-3h obtains load C o-MoS2/
The functionalization Hydrobon catalyst of LDHS.
Preferably, described solvent be ethylene glycol or second diether, ionic liquid be 1-methyl-3-carboxyethyl imidazoles Tetrafluoroboric acid
Salt, or 1-ethyl-3-methylimidazole tetrafluoroborate, ionic liquid is 0. 2-10:1 with the mol ratio of Mo.
Co-MoS2In/LDHS, MoS2Close monolayer of putting, and the MoS of preparation is formed on the surface of houghite carrier2Nanometer material
Material has the grain size of 3-8nm, and overall based on catalyst, metal Co content is 5-15wt%, MoS2Content is 5-15wt%.Institute
Stating alkaline solution is sodium hydroxide or ammonia spirit.
Described molybdate is four thio ammonium molybdate, and its molar concentration is 0.05-2mol/l, preferably 0.5-1mol/l.
Described reducing agent is oxammonium hydrochloride., hydrazine hydrate or sodium borohydride.
The main advantages of the present invention and be: use functionalized ion liquid to prepare molybdenum bisuphide and be carried on houghite surface,
Gained composite of the present invention, with molybdenum bisuphide and the structure of houghite and performance advantage, in synthetic system, saves
Vulcanizing agent and the sulfidation of molybdate precursor, directly from raw material control, be aided with ethylene glycol/second two ether solvents, utilize solvent
Effect improves the dispersibility of nano molybdenum disulfide, optimizes the particle size uniformity of molybdenum bisuphide, the wherein chi of nano molybdenum disulfide
Very little particle diameter is 3-8 nanometer.And add auxiliary agent cobalt component, increase the hydrogenation activity of system further.Present invention uses ionic liquid
Co-MoS prepared by body2/ LDHS, is respectively provided with fabulous dispersibility and catalysis in polarity, nonpolar catalystic converter system
Activity.
Existing research there is people have studied ionic liquid and prepare MoS2Hydrogenation catalyst, but this catalyst is the most active
Component, it is wear-resisting, resistance to compression effect is the most not enough, it is impossible to keep longtime running hydrogenation effect, Co-MoS prepared by the application2/
LDHS not only combines active component Co and MoS2, adjusted the mutual synergism of the two by preparation process so that activity group
Divide and mutually promote, optimize hydrogenation process further, and active component and carrier houghite are in preparation process, ionic liquid
Simultaneously at preparation MoS2Process, and due in loading process also have ionic liquid existence, therefore, optimize and loaded
Journey so that catalyst can have preferably hydrogenation effect while, moreover it is possible to improve catalyst service life, directly utilize two
The dispersibility of molybdenum sulfide, catalyst has good thermostability, crushing resistance and heat stability.
Cobalt active component is the active metal used during hydrofinishing, HDM, hydrodenitrogeneration, the present invention
There is provided cobalt-nano molybdenum disulfide/houghite in heavy oil, extra heavy oil, the floating bed hydrogenation desulfurization of residual oil, hydrodenitrogeneration, add
Hydrogen Porous deproteinized bone, hydrogenation depitching reaction a kind of or any two above in be demonstrated by fabulous catalysis activity.
It is additionally, since the layer structure of houghite, with MoS2In loading process, there may be the MoO of a part3Occur,
But the present invention both take part in the preparation of molybdenum bisuphide by ionic liquid, and also subparticipation is to loading process, not only
The pore size distribution of composite can be regulated and controled, moreover it is possible to control the amphiphilic of catalyst, expand the field of application, optimize use condition；
And make molybdenum oxide content in catalyst be less than 10%. Co-MoS2/ LDHS has loose structure, obtains the straight of nanoparticle
The nano material of footpath 20-80nm, and specific surface area can reach 450-600m2/ g, not only improves the dispersive property of molybdenum bisuphide,
The hydrodesulfurization effect of catalyst can also be optimized further.In order to further optimize the effect of hydrodesulfurization, the present invention also enters
One step has loaded certain cobalt, can optimize the effect that catalyst hydrogenation is refined.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further detailed explanation.
Embodiment 1
(1) preparation of nano molybdenum disulfide: adding concentration in solvent ethylene glycol is 0.05mol/l four thio ammonium molybdate, 1-first
Base-3-carboxyethyl tetrafluoroborate stirs, and is subsequently adding appropriate reducing agent hydrazine hydrate, stirs, be configured to
Initial reaction mixture is also transferred in Autoclaves for synthesis；Ionic liquid is 1:1 with the mol ratio of Mo；
(2) MoS2Load houghite: by ZnCl2、FeCl3And FeCl2Being dissolved into respectively in water, being configured to concentration is 1mol/L
Solution, by the mixing of three kinds of solution, keep Zn2+: Fe2+: Fe3+Mol ratio be 2:1:1, in 80 DEG C of water-baths of constant temperature instill one
Quantitative sodium hydroxide solution, adjusts system PH=8-11, reacts 2h, aging 12h, is formed in this process and have layer structure
Houghite precipitation, precipitate and separate, deionization wash 3 times, at a temperature of 550 DEG C calcine 2h；Then the class water that will obtain
Talc dispersion is to containing MoS2Synthesis reactor, add deionized water, hydro-thermal reaction 12h at keeping 200 DEG C, cool down, centrifugation,
Washing, solid product, washing, it is dried, obtains nanometer MoS2/ LDHS composite nano materials.
(3) nanometer MoS2/ LDHS composite nano materials is immersed in 0.1mol/l cobalt nitrate solution, stirs,
Standing 2 hours, aging 10 hours, filter, be dried, 500 DEG C of roasting 2h obtain load C o-MoS2The functionalization hydrogenation essence of/LDHS
Catalyst processed.Wherein overall based on catalyst, Co content is 10wt%, MoS2Content is 10wt%.
Embodiment 2
(1) preparation of nano molybdenum disulfide: add four thio ammonium molybdate, 1-ethyl-3-methylimidazole tetrafluoro boron in ethylene glycol
Hydrochlorate stirs, and is subsequently adding appropriate sodium borohydride, stirs, and is configured to initial reaction mixture and is transferred to high pressure
In synthesis reactor；The molar concentration of four thio ammonium molybdate is 0.8mol/l;
(2) MoS2Load houghite LDHS: by ZnCl2、FeCl3And FeCl2Being dissolved into respectively in water, being configured to concentration is
The solution of 2mol/L, by three kinds of solution mixing, keeps Zn2+: Fe2+: Fe3+Mol ratio be 3:2:1, in 80 DEG C of water-baths of constant temperature
Instill a certain amount of ammonia spirit, adjust system PH=8-10, react 2h, aging 12h, formed in this process and there is stratiform knot
The houghite precipitation of structure, precipitate and separate, deionization is washed 3 times, calcines 2h at a temperature of 500 DEG C；Houghite is disperseed
To containing MoS2Synthesis reactor, add deionized water, hydro-thermal reaction 12h at keeping 200 DEG C, cooling, centrifugation, wash, Gu
Body product, washing, it is dried, obtains nanometer MoS2/ LDHS composite nano materials.MoS2The mass ratio of/LDHS is 1:10.
(3) nanometer MoS2/ LDHS composite nano materials is immersed in 0.1mol/l cobalt nitrate solution, stirs,
Standing 2 hours, aging 12 hours, filter, be dried, 450 DEG C of roasting 3h obtain load C o-MoS2The functionalization hydrogenation essence of/LDHS
Catalyst processed.Wherein overall based on catalyst, Co content is 8wt%, MoS2Content is 15wt%.
Embodiment 3
(1) preparation of nano molybdenum disulfide: add four thio ammonium molybdate, 1-ethyl-3-methylimidazole tetrafluoro boron in second diether
Hydrochlorate stirs, and is subsequently adding appropriate sodium borohydride, stirs, and is configured to initial reaction mixture and is transferred to high pressure
In synthesis reactor；The molar concentration of four thio ammonium molybdate is 0.8mol/l.
(2) MoS2Load houghite LDHS: by ZnCl2、FeCl3And FeCl2It is dissolved into respectively in water, is configured to concentration
For the solution of 2mol/L, by three kinds of solution mixing, keep Zn2+: Fe2+: Fe3+Mol ratio be 3:2:1, in 80 DEG C of water-baths of constant temperature
A certain amount of ammonia spirit of middle instillation, adjusts system PH=8-10, reacts 2, h, aging 12h, is formed in this process and have stratiform
The houghite precipitation of structure, precipitate and separate, deionization is washed 3 times, calcines 2h at a temperature of 500 DEG C；Houghite is divided
It is dissipated to containing MoS2Synthesis reactor, add deionized water, hydro-thermal reaction 12h at keeping 200 DEG C, cooling, centrifugation, wash,
Solid product, washing, it is dried, obtains nanometer MoS2/ LDHS composite nano materials.
(3) nanometer MoS2/ LDHS composite nano materials is immersed in 0.1mol/l cobalt nitrate solution, stirs,
Standing 2 hours, aging 12 hours, filter, be dried, 450 DEG C of roasting 3h obtain load C o-MoS2The functionalization hydrogenation essence of/LDHS
Catalyst processed.Wherein overall based on catalyst, Co content is 10wt%, MoS2Content is 15wt%.
Comparative example 1
Being added without ionic liquid, other parameters are with embodiment 1.
Comparative example 2
Being added without Co component, other parameters are with embodiment 1.
Application examples
The present invention is by Co-MoS2/ LDHS is for Canada's oil sands bitumen floating bed hydrogenation reaction test catalyst activity.Catalyst
In the case of usage amount (in terms of molybdenum bisuphide)≤100ppm, desulfurization degree can reach 99%, asphaltene removal > 99%.And it is permissible
Amplify for industry, it is achieved catalyst longtime running non-inactivation.The character of Canada's oil sands bitumen is more severe, and difficulty of processing is remote
Far above common heavy oil or heavy oil.Hydrogenation the results are shown in Table 1.
Table 1 hydrodesulfurization effect and other test indexs
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Conversion ratio, % | 82.2 | 82.9 | 82.5 | 59.9 | 59.1 |
| Light oil yield, % | 65.1 | 65.9 | 62.5 | 50.2 | 44.6 |
| Distillate yield, % | 81.2 | 82.5 | 81.1 | 60.4 | 50.4 |
| Liquid yield, % | 85.3 | 84.4 | 80.2 | 71.9 | 69.4 |
| Asphalitine takes off rate, % | 98.0 | 97.2 | 98.0 | 80.5 | 77.4 |
Yield of light oil=less than 350 DEG C of fraction section quality/raw oil quality × 100%
Distillate yield=less than 550 DEG C of fraction section quality/raw oil quality × 100%
Liquid yield=liquid product mass/raw oil quality × 100%
Conversion ratio=less than 550 DEG C of constituent mass (gassiness)/raw oil quality × 100%
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any familiar
Those skilled in the art in the technical scope that disclosed herein, the change that can expect without creative work or replace
Change, all should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Protection domain be as the criterion.
Claims (8)
1. a Co-MoS2/ LDHS Hydrobon catalyst, it is characterised in that use the method for ionic liquid to obtain difunctional
Co-MoS2Load hydrotalcite-like materials LDHS catalyst, described MoS2Formed on the surface of houghite carrier and close put monolayer；Institute
State Co-MoS2/ LDHS has loose structure, and catalyst diameter is 20-80nm, and specific surface area is 450-600m2/ g, nanometer MoS2
Particle diameter is 3-8nm.
2. catalyst as claimed in claim 1, it is characterised in that the preparation process of nano molybdenum disulfide is: add in solvent
Enter tetrathiomolybdate, ionic liquid stirs, and is subsequently adding appropriate reducing agent, stirs, is configured to primary response
Mixture is also transferred in Autoclaves for synthesis.
3. catalyst as claimed in claim 1 or 2, described in its feature, described ionic liquid is 1-methyl-3-carboxyethyl imidazoles
Tetrafluoroborate, or 1-ethyl-3-methylimidazole tetrafluoroborate, ionic liquid is 0. 2-10:1 with the mol ratio of Mo.
4. catalyst as claimed in claim 2, it is characterised in that described solvent is ethylene glycol or second diether, described reducing agent
For in oxammonium hydrochloride., hydrazine hydrate or sodium borohydride one or more.
5. the catalyst as described in claim 2 or 4, it is characterised in that described molybdate is four thio ammonium molybdate, and its mole dense
Degree is 0.05-2mol/l, preferably 0.5-1mol/l.
6. catalyst as claimed in claim 1, it is characterised in that the preparation process of houghite is: by ZnCl2、FeCl3With
FeCl2It is dissolved into respectively in water, is configured to the solution that concentration is 1～2mol/L, by three kinds of solution mixing, keep Zn2+: Fe2+:
Fe3+Mol ratio be (2～4): (1～2): 1, constant temperature 70～80 DEG C of water-baths instills a certain amount of alkaline solution, reaction 2～
3h, aging 12～24h, form the houghite precipitation with layer structure, precipitate and separate, deionization washing 2 in this process
～3 times, at a temperature of 400～550 DEG C, calcine 1-5h；Houghite is dispersed to containing MoS2Synthesis reactor, add go from
Sub-water, hydro-thermal reaction 12h at keeping 150-200 DEG C, cooling, centrifugation, washing, solid product, washing, it is dried, is received
Rice MoS2/ LDHS composite nano materials.
7. catalyst as claimed in claim 6, it is characterised in that the load step of metallic cobalt is: nanometer MoS2/ LDHS is combined
Nano material is immersed in 0.05-0.1mol/l cobalt nitrate solution, stirs, and stands 2-5 hour, and aging 10-12 is little
Time, filtering, be dried, 400-500 DEG C of roasting 2-3h obtains load C o-MoS2/LDHS。
8. the catalyst as described in claim 1-7 is arbitrary is used for heavy oil, extra heavy oil, the floating bed hydrogenation subtractive process of residual oil
In.
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| CN109174132A (en) * | 2018-09-19 | 2019-01-11 | 天津大学 | The catalyst and preparation method of aromatic hydrocarbon are prepared for Catalytic lignin model compound reaction |
| CN112934243A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Spherical non-supported suspension bed hydrodesulfurization catalyst, preparation and application |
| CN112371141A (en) * | 2020-12-10 | 2021-02-19 | 福州大学 | Catalytic gasoline hydrodesulfurization catalyst and preparation method thereof |
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