CN106268872A - A kind of support type MoS2/ LDHS Hydrobon catalyst and application - Google Patents
A kind of support type MoS2/ LDHS Hydrobon catalyst and application Download PDFInfo
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- CN106268872A CN106268872A CN201610568683.XA CN201610568683A CN106268872A CN 106268872 A CN106268872 A CN 106268872A CN 201610568683 A CN201610568683 A CN 201610568683A CN 106268872 A CN106268872 A CN 106268872A
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- CN
- China
- Prior art keywords
- ldhs
- mos
- hydrobon catalyst
- houghite
- ionic liquid
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052961 molybdenite Inorganic materials 0.000 title claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 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
- 239000003921 oil Substances 0.000 claims description 14
- -1 Ethyl imidazol Chemical compound 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000295 fuel oil Substances 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 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
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 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
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000463 material 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
- 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
- 150000001768 cations Chemical class 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [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 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000002105 nanoparticle Substances 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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000003839 salts Chemical group 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 11
- 239000011733 molybdenum Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000005486 sulfidation Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method 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
- 230000000052 comparative effect Effects 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-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
-
- B01J35/40—
-
- B01J35/615—
-
- B01J35/617—
-
- 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
Abstract
The present invention relates to hydrodesulfurization catalytic field, particularly relate to support type MoS prepared by a kind of ionic liquid2/ LDHS Hydrobon catalyst, gained composite is with 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 ethylene glycol solvent, improves the dispersibility of nano molybdenum disulfide, catalyst has good thermostability, crushing resistance and heat stability.
Description
Technical field
The present invention relates to hydrodesulfurization field, particularly relate to a kind of support type MoS using ionic liquid to prepare2/LDHS
Hydrobon catalyst and application thereof.
Background technology
In recent years, along with the quick increase of automobile pollution, the demand of fuel oil is also being increased year by year, but in fuel oil
The oxysulfide that formed in combustion of sulfur-containing compound air is caused serious pollution, PM2.5 can be caused
Pollute and then cause haze weather.Standard of fuel and developed country that China is current also have certain distance, according to Chinese Ministry of Environmental Protection's introduction, warp
Even if testing existing automobile not transform, being only to use state five regular fuel, vehicle exhaust at least subtracts about the discharge of pollutant
Few 10%.Therefore, fuel oil realizes one of low-cost high-efficiency deep desulfuration focus becoming fuel oil field of refinement.
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 at absorbent fields equally.Houghite (writing a Chinese character in simplified form LDH) is a class two-dimensional
Nanometer anionic clay, its composition formula is represented by [M1-x 2+Mx 3+(OH)2]x+(An-)x/n·mH2O, wherein M2+Refer to bivalence gold
Belong to cation, M3+Referring to trivalent metal cation, x is M2+With M3+Mol ratio, A n-For interlayer can the anion of stable existence, tool
There is hydrotalcite layered structure, because its lamella is elementary composition and charge density is adjustable, interlayer guest molecule, crystalline size are controlled, with
And the advantage such as bio-toxicity is low, present at numerous areas such as organic catalysis, polymeric additive, biological medicine, environmental conservation
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, obtains can be used in heavy oil
The catalyst of hydrodesulfurization.Described MoS2In/LDHS, MoS2Formed on the surface of houghite carrier and close put monolayer.
MoS2The mass ratio of/LDHS is 1-5:10-15.
The preparation method of heavy-oil hydrogenation catalyst 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 MgCl2、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 Mg2+: 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 synthesis reactor, adds deionized water, hydro-thermal reaction 12h at keeping 150-200 DEG C, cooling, be centrifuged
Separate, washing, solid product, washing, be dried, obtain nanometer MoS2/ LDHS composite nano materials.
Preferably, described solvent be ethylene glycol, ionic liquid be 1-methyl-3-carboxyethyl tetrafluoroborate, or 1-
Ethyl-3-methylimidazole tetrafluoroborate, ionic liquid is 0. 2-10:1 with the mol ratio of Mo.
MoS2In/LDHS, MoS2Formed on the surface of houghite carrier and close put monolayer. MoS2The mass ratio of/LDHS is
1-5:10-15.Described 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.
Further, the present invention can also load a small amount of W metal (based on catalyst, W metal content 1-5wt%), will
Obtain nanometer MoS2/ LDHS composite nano materials is immersed in 0.05-0.1mol/l nickel nitrate solution, stirs, quiet
Putting 2-5 hour, aging 10-12 hour, filter, be dried, 400-500 DEG C of roasting 2-3h obtains loading Ni-MoS2The function of/LDHS
Change Hydrobon catalyst.
The present invention compared with prior art, the main advantages of the present invention and is: use functionalized ion liquid to prepare curing
Molybdenum is carried on houghite surface, and gained composite of the present invention is excellent with molybdenum bisuphide and the structure of houghite and performance
Gesture, in synthetic system, eliminates the sulfidation of vulcanizing agent and molybdate precursor, directly from raw material control, is aided with ethylene glycol
Solvent, 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.Present invention uses the nano molybdenum disulfide/hydrotalcite-like materials prepared by ionic liquid, polarity,
Nonpolar catalystic converter system is respectively provided with fabulous dispersibility and catalysis 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, MoS prepared by the application2/ LDHS is not
But combine MoS2With houghite, and in preparation process, ionic liquid is simultaneously at preparation MoS2Process, and due to
Loading process also has the existence of ionic liquid, therefore, optimizes loading process so that catalyst can have and is preferably hydrogenated with
While effect, moreover it is possible to improving the service life of catalyst, directly utilize the dispersibility of molybdenum bisuphide, catalyst has good
Thermostability, crushing resistance and heat stability.
Cobalt-nano molybdenum disulfide/houghite that the present invention provides takes off at the floating bed hydrogenation of heavy oil, extra heavy oil, residual oil
Sulfur, hydrodenitrogeneration, hydrogenation aromatics-removing, hydrogenation depitching reaction a kind of or any two above in be demonstrated by fabulous catalysis and live
Property.
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%. MoS2/ LDHS has loose structure, obtains the diameter of nanoparticle
The nano material of 20-80nm, and specific surface area can reach 450-600m2/ g, not only improves the dispersive property of molybdenum bisuphide, also
The hydrodesulfurization effect of catalyst can be optimized further.In order to further optimize the effect of hydrodesulfurization, the present invention also enters one
Step has loaded certain nickel, finds the effect of the hydrodesulfurization not only played, it is also possible to optimize the effect of catalyst hydrogenation denitrogenation.
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 MgCl2、FeCl3And FeCl2Being dissolved into respectively in water, being configured to concentration is 1mol/L
Solution, by the mixing of three kinds of solution, keep Mg2+: 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 houghite obtained is dispersed to synthesis reactor, adds deionized water, hydro-thermal reaction 12h at keeping 200 DEG C, cold
But, centrifugation, washing, solid product, washing, it is dried, obtains nanometer MoS2/ LDHS composite nano materials.Wherein MoS2/
The mass ratio of LDHS is 5:15.
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 MgCl2、FeCl3And FeCl2Being dissolved into respectively in water, being configured to concentration is
The solution of 2mol/L, by three kinds of solution mixing, keeps Mg2+: 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 2, h, 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 dispersed to synthesis reactor, adds 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.MoS2The mass ratio of/LDHS is 1:10.
Embodiment 3
(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 MgCl2、FeCl3And FeCl2Being dissolved into respectively in water, being configured to concentration is
The solution of 2mol/L, by three kinds of solution mixing, keeps Mg2+: 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 2, h, 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 dispersed to synthesis reactor, adds 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.MoS2The mass ratio of/LDHS is 1:10.
(3) nanometer MoS will be obtained2/ LDHS composite nano materials is immersed in 0.05-0.1mol/l nickel nitrate solution, fills
Dividing and stir, stand 2-5 hour, aging 10-12 hour, filter, be dried, 500 DEG C of roasting 3h obtain loading Ni-MoS2/
The functionalization Hydrobon catalyst of LDHS.Based on catalyst, W metal content 5wt%.
Comparative example 1
Preparing molybdenum bisuphide only with ionic liquid, do not use LDHS, other parameters are with embodiment 1.
Application examples
The present invention is by MoS2/ LDHS tests catalyst activity for Kelamayi super-viscous oil for floating bed hydrogenation reaction unification.
In the case of catalyst usage amount (in terms of molybdenum bisuphide)≤80ppm, desulfurization degree can reach 99%, asphaltene removal > 99%.
Significantly better than using merely MoS2Hydrogenation effect.400g Kelamayi super-viscous oil, catalyst 5g and 1.0g sodium sulfide are added
Enter in High Temperature High Pressure stirred tank, stir, sealing, hydrogen first pressing 9.0MPa, at 350 DEG C, react 15min；It is continuously heating to
430 DEG C, react 30min.React complete about 180 DEG C releases, simultaneously meter gaseous amount sampling analysis gas composition.
Table 1 Kelamayi super-viscous oil nature parameters
| Project | Kelamayi super-viscous oil |
| Density (20 DEG C, g/cm3) | 1.21 |
| 100 DEG C of kinematic viscositys, mm2/s | 3257 |
| Saturated point, wt% | 22.4 |
| Aromatic hydrocarbons, wt% | 32.8 |
| Colloid, wt% | 26.8 |
| Asphalitine, wt% | 18.0 |
| Carbon residue, wt% | 19.8 |
| Element S is analyzed, wt% | 5.5 |
| Element N analyzes, wt% | 1.2 |
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%
Table 2 hydrodesulfurization effect and other test indexs
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 2 |
| Conversion ratio, % | 86.2 | 88.9 | 89.5 | 75.1 |
| Light oil yield, % | 69.1 | 66.9 | 69.5 | 46.2 |
| Distillate yield, % | 80.2 | 88.1 | 89.1 | 70.4 |
| Liquid yield, % | 85.3 | 82.4 | 86.2 | 74.9 |
| Desulfurization degree, % | 99.1 | 98.9 | 99.0 | 80.1 |
| Asphalitine takes off rate, % | 99.0 | 99.2 | 98.9 | 82.4 |
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 (9)
1. a MoS2/ LDHS Hydrobon catalyst, it is characterised in that use the method for ionic liquid to obtain MoS2Load class
Hydrotalcite material LDHS, described MoS2In/LDHS, MoS2Formed on the surface of houghite carrier and close put monolayer；Described MoS2/
LDHS has loose structure, the nano material of the diameter 20-80nm of nanoparticle, and specific surface area is 450-600m2/g。
2. Hydrobon catalyst as claimed in claim 1, it is characterised in that the preparation process of nano molybdenum disulfide is: to
Add tetrathiomolybdate in solvent, ionic liquid stirs, and is subsequently adding appropriate reducing agent, stirs, is configured to
Initial reaction mixture is also transferred in Autoclaves for synthesis, MoS2The mass ratio of/LDHS is about 1-5:10-15.
3. Hydrobon catalyst as claimed in claim 1 or 2, described in its feature, described ionic liquid is 1-methyl-3-carboxylic
Ethyl imidazol(e) tetrafluoroborate, or 1-ethyl-3-methylimidazole tetrafluoroborate, ionic liquid is 0. 2-with the mol ratio of Mo
10:1.
4. Hydrobon catalyst as claimed in claim 2, it is characterised in that described solvent is ethylene glycol, and reducing agent is salt
Acid azanol, hydrazine hydrate or sodium borohydride.
5. the Hydrobon catalyst as described in claim 2 or 4, it is characterised in that described molybdate is four thio ammonium molybdate,
Its molar concentration is 0.05-2mol/l, preferably 0.5-1mol/l.
6. Hydrobon catalyst as claimed in claim 1 or 2, it is characterised in that bivalence gold in described LDHS houghite
Belong to ion M2+For Mg2+、Fe2+, trivalent metal cation M3+For Fe3+ 。
7. Hydrobon catalyst as claimed in claim 6, it is characterised in that the preparation process of houghite is: by MgCl2、
FeCl3And 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 Mg2 +: Fe2+: Fe3+Mol ratio be (2～4): (1～2): 1, in constant temperature 70～80 DEG C of water-baths, instill a certain amount of alkaline solution,
Reaction 2～3h, aging 12～24h, in this process formed have layer structure houghite precipitation, precipitate and separate, go from
Son washing 2～3 times, calcines 1-5h at a temperature of 400～550 DEG C.
8. as claimed in claim 6 Hydrobon catalyst, it is characterised in that described alkaline solution be sodium hydroxide or ammonia molten
Liquid.
9. MoS as described in claim 1-8 is arbitrary2/ LDHS Hydrobon catalyst is used for heavy oil, extra heavy oil, the suspension bed of residual oil
Hydrodesulfurization reaction.
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Cited By (2)
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| CN112934244A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Non-supported suspension bed hydrodesulfurization catalyst, preparation and application |
| CN113461061A (en) * | 2021-07-28 | 2021-10-01 | 洛阳申雨钼业有限责任公司 | Preparation method of high-purity molybdenum disulfide |
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