CN109794236A - A kind of preparation of the nucleocapsid catalyst of efficient prepared from benzene and hydrogen for cyclohexene - Google Patents
A kind of preparation of the nucleocapsid catalyst of efficient prepared from benzene and hydrogen for cyclohexene Download PDFInfo
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- CN109794236A CN109794236A CN201910076211.6A CN201910076211A CN109794236A CN 109794236 A CN109794236 A CN 109794236A CN 201910076211 A CN201910076211 A CN 201910076211A CN 109794236 A CN109794236 A CN 109794236A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title abstract description 120
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title abstract description 70
- 239000001257 hydrogen Substances 0.000 title abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 12
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000011258 core-shell material Substances 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 9
- OSKSAMGBRKRQOZ-UHFFFAOYSA-N benzene cyclohexene Chemical compound C1CCC=CC1.C1CCC=CC1.C1=CC=CC=C1 OSKSAMGBRKRQOZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910001868 water Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000002525 ultrasonication Methods 0.000 claims description 8
- 239000012456 homogeneous solution Substances 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910001887 tin oxide Inorganic materials 0.000 claims 1
- 241000894007 species Species 0.000 abstract description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002078 nanoshell Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- -1 amino cation Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation methods of one kind (Ru/MeOx)@m-MeOx core-shell structure bifunctional catalyst, nuclear phase Ru/MeOx and shell phase m-MeOx form suitable interfacial catalysis center, the ruthenium-based catalyst of this method preparation has very high dispersibility, make the Dissociative of benzene more easily at a lower temperature, the conversion for improving benzene is forthright；Hydrophilic m-MeOx shell phase makes cyclohexene be easier to be desorbed on shell, it prevents from further adding hydrogen, enhance cyclohexene selectivity, its core-shell structure can also reduce the loss of active specy, and catalyst is made to have more stability, resistance to mass tranfer can also be reduced simultaneously, and excellent composite performance can be applied in the reaction of partial hydrogenation of benzene cyclohexene, have very high selectivity and yield.Preparation method of the present invention is simple, mild condition, is easy to repeat, is conducive to large-scale industrial production.
Description
Technical field
The present invention relates to catalyst technical fields, and specifically one kind is using metal Ru as core, and loads on it
Hydrophilic oxide (MeOx) forms double activated component, then using these hydrophilic oxides as meso-porous nano shell (m-MeOx),
The preparation method of the catalyst of core-shell structure is formed, is applied to partial hydrogenation of benzene cyclohexene and reacts.
Background technique
Cyclohexene is a kind of very important Organic Chemicals, has active c=c double bond, can be widely applied to polycyclic
The production of other fine chemical products such as olefine resin, rubber chemicals, high-knock rating gasoline stabilizer and nylon 6.Due to cyclohexene
As the widely used of raw material, so further the more economical and eco-friendly cyclohexene production line of exploitation is widely paid close attention to.Benzene
Cheap, abundance, direct synthesizing cyclohexene can be used to.Benzene selective adds hydrogen cyclohexene because of its atom utilization
It is high, safety is good, economic performance is high and by-product is few etc., and advantages get more and more people's extensive concerning.
The research reacted for benzene selective plus hydrogen cyclohexene originates in or so nineteen thirties, at that time for
Benzene selective adds the research of hydrogen cyclohexene to only reside in guess；Until nineteen fifty-seven, hexamethylene is detected in the product finally
Dilute presence.This is that cyclohexene truly is made by the method for partial hydrogenation of benzene for the first time, also demonstrates this technique
Feasibility；1973, Drinkard etc. had found with RuCl3The selectivity of cyclohexene is obviously improved as catalyst, yield can
Up to 30%, prepared from benzene and hydrogen is made to have certain breakthrough for cyclohexene；1988, Japanese industrial group, Asahi Chemical Industry took the lead in Shui Dao
The production line through cyclohexene hydration cyclohexanol by benzene for establishing first 60,000 tons of annual output in the world, realizes benzene and adds
The industrialized production of hydrogen cyclohexene, but this technology is monopolized by Japanese Asahi Kasei Corporation, and this strongly limits China's cyclohexene
Large-scale production.In recent years, by the research of major colleges and universities and scientific research institutions, China is in terms of partial hydrogenation of benzene cyclohexene
Obtain significant progress.However compared with foreign technology, the produced catalyst in China still has no small gap.How ring is made
The stable yield of hexene improve and maintain 50% or more be still presently relevant technical study primary goal.Carry out about benzene
Partial hydrogenation prepares the research in terms of cyclohexene, has a very important significance especially for the exploration in terms of catalyst.
In advanced field of nanocomposite materials, core-shell structure is more and more by the favor of scientific research personnel.This is because
Different components can be effectively bonded together by core-shell structure on nanoscale, and the design dependent on core and shell synthesizes,
To realize the synergistic effect between multicomponent.Due to this multilevel structure, in redox catalysis, can both it prevent depth from adding
Hydrogen is also possible to prevent deep oxidation, generally has very high selectivity and conversion ratio.Furthermore this structure generates shell to core
Protective effect, it is possible to reduce the loss of active specy, and so that catalyst is had more stability, while the porous structure of shell can also be reduced
Resistance to mass tranfer.So core-shell structure has good research significance and application prospect, but develop simplicity and general nucleocapsid knot
Structure synthetic method realizes that accurate control shell thickness, uniformity and functionality still have significant challenge.
Summary of the invention
The purpose of the present invention is being directed to the lower yield of cyclohexene and selectivity, one kind is provided with metal Ru and hydrophily oxygen
Compound (MeOx) is that core can be applied using these hydrophilic oxides as the core-shell structure bifunctional catalyst of meso-porous nano shell
It is reacted in partial hydrogenation of benzene cyclohexene, there is very high yield.
Method includes the following steps:
1. basic step
(1) preparation of Ru/MeOx: MeOx:RuCl is matched by feed molar3·3H2O=60 ~ 90:1, by MeOx at 60 ~ 100 DEG C
Baking oven in be dried overnight, and be dispersed in RuCl under ultrasonication3·3H2In O aqueous solution, 2 ~ 10 h are then vigorously stirred,
By being centrifugated suspension obtained, then washing, drying, reduction obtain Ru/MeOx particle；
(2) preparation of Ru/MeOx@m-MeOx: Ru/MeOx is dispersed in water to form suspending liquid A；Template is dissolved in distillation
In water, HCl solution is then added, stirs the mixture for 30 ~ 60 minutes, forms homogeneous solution B；Ru/ is sequentially added into solution B
MeOx suspending liquid A and (BuO)4Me is subsequently agitated for, and is filtered, and is washed, dry, calcining, to obtain Ru/MeOx@m-MeOx catalysis
Agent.
2. in the step (1), MeOx:RuCl3·3H2O=60 ~ 80:1, the drying temperature are 50 ~ 80 DEG C, and the time is
10~12h；The volume ratio of reducing gas is H during described2: N2=1:8 ~ 15, reduction temperature are 350 ~ 450 DEG C, and the recovery time is
3~6 h。
3. in the step (2), mole group of liquid phase feed becomes template: HCl:(BuO)4Me:H2O=1.0:10 ~ 20:
5.0 ~ 12.0:620.0 ~ 850.0.
4. in the step (2), the mass fraction of Ru/MeOx water slurry is 6wt% ~ 10wt%, the quality of HCl solution
Score is 32wt% ~ 38wt%.
5. in the step (2), whipping temp is 20 ~ 30 DEG C, mixing speed is 300 ~ 350 r/min, mixing time
For 15 ~ 20 h.
6. in the step (2), dry temperature is 313K ~ 365K, and calcination temperature is 773 ~ 873K, calcination time is 4 ~
10 h。
7. the MeOx(graphite oxide in the step (1)) it is silica, titanium dioxide, stannic oxide and zirconium oxide
One or more of.
8. the template in the step (2) is ten alkyl trimethyl ammonium bromides, cetyl trimethylammonium bromide, 14
One or more of alkyl trimethyl ammonium bromide.
9. (BuO) in the step (2)4Me is tetra-n-butyl titanate, four N-butyl of silicic acid, four N-butyl of stannic acid and zirconium
One or more of sour four N-butyls.
10. obtained catalysis material can be used for the reaction of partial hydrogenation of benzene cyclohexene.
Compared with prior art, the present invention there is apparent advantage, as can be known from the above technical solutions: preparing one kind with Ru/
MeOx is nuclear phase, and mesoporous m-MeOx is the new type structure of hud catalyst of shell phase, and the construction of nuclear phase Ru/MeOx promotes metal Ru to have
There are dispersibility and uniformity well, monatomic utilization rate is higher, and nuclear phase Ru/MeOx forms solid-solution structures, and then generates oxygen
Vacancy and special surface L acid-base property improve H as more suitable hydrogenation sites2Utilization rate, and then improve benzene conversion ratio；
Nuclear phase Ru/MeOx and shell phase m-MeOx form suitable interfacial catalysis center, are the Dissociative of benzene more easily at a lower temperature,
The conversion for improving benzene is forthright；Hydrophilic MeOx shell phase makes cyclohexene be easier to be desorbed on shell, prevents from further adding hydrogen, enhancing
Cyclohexene selectivity, inhibits by-product to generate；The hierarchical structure construction of micro--mesoporous system weakens the diffusion limitation of molecule, reduces
Mass transfer and heat transmission resistance enhance the stability of catalyst, extend catalyst life.I.e. with the obtained Ru/MeOx@m- of the present invention
MeOx catalyst with core-casing structure is applied in preparing cyclohexene from benzene added with hydrogen technique, is not only had compared with high reaction activity and hydrogen utilization ratio,
Also there is higher cyclohexene selectivity, while the stability of catalyst can also be enhanced.
Specific embodiment
The present invention provides the preparation method of one kind (Ru/MeOx)@m-MeOx core-shell structure bifunctional catalyst, and feature exists
In, method includes the following steps:
(1) preparation of Ru/MeOx: MeOx:RuCl is matched by feed molar3·3H2O=60 ~ 90:1, by MeOx at 60 ~ 100 DEG C
Baking oven in be dried overnight, and be dispersed in RuCl under ultrasonication3·3H2In O aqueous solution, 2 ~ 10 h are then vigorously stirred,
By being centrifugated suspension obtained, then washing, drying, reduction obtain Ru/MeOx particle；
(2) preparation of Ru/MeOx@m-MeOx: Ru/MeOx is dispersed in water to form suspending liquid A；Template is dissolved in distillation
In water, HCl solution is then added, stirs the mixture for 30 ~ 60 minutes, forms homogeneous solution B；Ru/ is sequentially added into solution B
MeOx suspending liquid A and (BuO)4Me is subsequently agitated for, and is filtered, and is washed, dry, calcining, to obtain Ru/MeOx@m-MeOx sample
Product.
According to the method for the present invention, hydrophilic oxide (MeOx) as described in step (1) can be well known in the art
Various high-purities solid silica, titanium dioxide, stannic oxide and zirconium oxide.Specifically, silica can be
A200, titanium dioxide can be anatase, and zirconium oxide can be Soviet Union's stone, and stannic oxide can be tetragonal crystal system stannic oxide.
According to the method for the present invention, the organic quaternary ammonium salt that template described in step (2) can be well known in the art
Class can be specifically ten alkyl trimethyl ammonium bromides, tetradecyltrimethylammonium bromide, cetyl trimethylammonium bromide
One or more of.Preferably cetyl trimethylammonium bromide.
According to the method for the present invention, reduction temperature described in step (1) is preferably 350 ~ 400 DEG C, and the time is 3 ~ 5 h.
According to the method for the present invention, the restoring method as described in step (1) is known to those skilled in the art
Method.
According to the method for the present invention, mixing speed is 300 ~ 350 r/min in step (2), and mixing time is 15 ~ 20
h。
According to the method for the present invention, washing described in the step (2), drying, method for calcinating are those skilled in the art
Method well known to member.After being washed 3 times for example, by using deionized water, dry 2 ~ 10 h at 60 DEG C.
Obtained catalysis material can be used for the reaction of partial hydrogenation of benzene cyclohexene.
Below by way of specific embodiment, the present invention will be described in detail, but the present invention is not restricted to following implementations
Example.
Reagent in following example 1 ~ 5, silicon source are purchased from Shanghai Shan Bo Industrial Co., Ltd., and organic formwork agent is purchased from West Asia
Reagent Co., Ltd, remaining reagent are purchased from Sinopharm Chemical Reagent Co., Ltd..
The mole of template in following embodiment is with TEA+(organic amino cation) meter；
Embodiment 1
The present embodiment is used to illustrate the preparation method of (Ru/MeOx)@m-MeOx core-shell structure bifunctional catalyst, including following step
It is rapid:
(1) Ru/ZrO2Preparation: by feed molar match ZrO2: RuCl3·3H2O=60:1, by 5.85 g ZrO2At 100 DEG C
Baking oven in be dried overnight, and be dispersed in RuCl under ultrasonication3·3H2In O aqueous solution (0.2082 g, 300 mL), so
After be vigorously stirred 3h.By being centrifugated suspension obtained, it is washed with deionized until AgNO3Reagent is not detected
Cl-, 12 h are then dried at 60 DEG C in air circulation oven.Then, at 400 DEG C, by sample in 10% H2(H2/
N2=1:9, v/v) 3 h of middle reduction, the rate of heat addition is 5 DEG C of min-1, obtain ZrO2The Ru particle of load；
(2) (Ru/ZrO2)@m-ZrO2Preparation: mole group of liquid phase feed become 1.0 CnTMAB:15.0 HCl:8.0
(BuO)4Zr:680.0H2O.By 3.74 g Ru/ZrO2It is dispersed in water to form the suspension of 10wt%.By 2.0 g
C16TMAB is dissolved in 33.7 g distilled water, and 8.35 g HCl solutions (36wt%) are then added.30 minutes are stirred the mixture for, shape
At clear homogeneous solution.Ru/ZrO is sequentially added into the solution2Suspension and 16.9 g (BuO)4Zr.Use magnetic agitation
Device is at room temperature with 20 h of the speed stirring mixture of 300-350r/min.Solid product is collected by filtration, is washed with water and ethyl alcohol
It washs for several times, it is then dry at 313K in air.It is remaining organic to remove that product is calcined to 6 h in air at 823K
Substance.
Use example: by 1 gained Ru/ZrO of embodiment2@m-ZrO2Catalyst with core-casing structure is applied in preparing cyclohexene from benzene added with hydrogen work
(reaction pressure: reaction temperature: 5.0 MPa 150 DEG C, react revolving speed: 1000 r/min, the body of benzene and water in reactant in skill
Product is than being 1:2, catalyst 1g, benzene 100ml, reaction time 1h), measure benzene conversion ratio 94.60%, cyclohexene selectivity
81.32%。
Embodiment 2
The present embodiment is used to illustrate the preparation method of (Ru/MeOx)@m-MeOx core-shell structure bifunctional catalyst, including following step
It is rapid:
(1) Ru/ZrO2Preparation: by feed molar match ZrO2: RuCl3·3H2O=70:1, by 5.85 g ZrO2At 100 DEG C
Baking oven in be dried overnight, and be dispersed in RuCl under ultrasonication3·3H2In O aqueous solution (0.1816 g, 300 mL), so
After be vigorously stirred 3h.By being centrifugated suspension obtained, it is washed with deionized until AgNO3Reagent is not detected
Cl-, 12 h are then dried at 60 DEG C in air circulation oven.Then, at 400 DEG C, by sample in 10% H2(H2/
N2=1:9, v/v) 3 h of middle reduction, the rate of heat addition is 5 DEG C of min-1, obtain ZrO2The Ru particle of load；
(2) (Ru/ZrO2)@m-ZrO2Preparation: mole group of liquid phase feed become 1.0 CnTMAB:15 HCl:8.0 (BuO)4Zr:680.0H2O.By 3.74 g Ru/ZrO2It is dispersed in water to form the suspension of 10wt%.By 2.0 g C16TMAB is dissolved in
In 33.7 g distilled water, 8.35 g HCl solutions (36wt%) are then added.It stirs the mixture for 30 minutes, is formed clear equal
Even solution.Ru/ZrO is sequentially added into the solution2Suspension and 16.9 g (BuO)4Zr.At room temperature using magnetic stirring apparatus
With the speed stirring mixture 20h of 300-350r/min.Solid product is collected by filtration, for several times with water and ethanol washing, then
It is dry at 313K in air.Product is calcined to 6h in air at 823K to remove remaining organic substance.
Use example: by 2 gained Ru/ZrO of embodiment2@m-ZrO2Catalyst with core-casing structure is applied in preparing cyclohexene from benzene added with hydrogen work
(reaction pressure: reaction temperature: 5.0 MPa 150 DEG C, react revolving speed: 1000 r/min, the body of benzene and water in reactant in skill
Product is than being 1:2, catalyst 1g, benzene 100ml, reaction time 1h), measure benzene conversion ratio 93.49%, cyclohexene selectivity 82
.96%。
Embodiment 3
The present embodiment is used to illustrate the preparation method of (Ru/MeOx)@m-MeOx core-shell structure bifunctional catalyst, including following step
It is rapid:
(1) Ru/TiO2Preparation: by feed molar match TiO2: RuCl3·3H2O=60:1, by 3.97 g TiO2At 100 DEG C
Baking oven in be dried overnight, and be dispersed in RuCl under ultrasonication3·3H2In O aqueous solution (0.2082 g, 300 mL), so
After be vigorously stirred 3h.By being centrifugated suspension obtained, it is washed with deionized until AgNO3Reagent is not detected
Cl-, 12 h are then dried at 60 DEG C in air circulation oven.Then, at 400 DEG C, by sample in 10% H2(H2/
N2=1:9, v/v) 3 h of middle reduction, the rate of heat addition is 5 DEG C of min-1, obtain TiO2The Ru particle of load；
(2) (Ru/TiO2)@m-TiO2Preparation: mole group of liquid phase feed become 1.0 CnTMAB:15.0 HCl:8.0
(BuO)4Ti:680.0H2O.By 3.74 g Ru/TiO2It is dispersed in water to form the suspension of 10wt%.By 2.0 g
C16TMAB is dissolved in 33.7 g distilled water, and 8.35 g HCl solutions (36wt%) are then added.30 minutes are stirred the mixture for, shape
At clear homogeneous solution.Ru/TiO is sequentially added into the solution2Suspension and 3.00 g (BuO)4Ti.Use magnetic agitation
Device is at room temperature with 20 h of the speed stirring mixture of 300-350r/min.Solid product is collected by filtration, is washed with water and ethyl alcohol
It washs for several times, it is then dry at 313K in air.It is remaining organic to remove that product is calcined to 6 h in air at 823K
Substance.
Use example: by 3 gained Ru/TiO of embodiment2@m-TiO2Catalyst with core-casing structure is applied in preparing cyclohexene from benzene added with hydrogen work
(reaction pressure: reaction temperature: 5.0 MPa 150 DEG C, react revolving speed: 1000 r/min, the body of benzene and water in reactant in skill
Product is than being 1:2, catalyst 1g, benzene 100ml, reaction time 1h), measure benzene conversion ratio 89.94%, cyclohexene selectivity
79.58%。
Embodiment 4
The present embodiment is used to illustrate the preparation method of (Ru/MeOx)@m-MeOx core-shell structure bifunctional catalyst, including following step
It is rapid:
(1) Ru/SiO2Preparation: by feed molar match SiO2: RuCl3·3H2O=60:1, by 2.85 g SiO2At 100 DEG C
Baking oven in be dried overnight, and be dispersed in RuCl under ultrasonication3·3H2In O aqueous solution (0.2082 g, 300 mL), so
After be vigorously stirred 3h.By being centrifugated suspension obtained, it is washed with deionized until AgNO3Reagent is not detected
Cl-, 12 h are then dried at 60 DEG C in air circulation oven.Then, at 400 DEG C, by sample in 10% H2(H2/
N2=1:9, v/v) 3 h of middle reduction, the rate of heat addition is 5 DEG C of min-1, obtain SiO2The Ru particle of load；
(2) (Ru/SiO2)@m-SiO2Preparation: mole group of liquid phase feed become 1.0 CnTMAB:15.0 HCl:8.0
(BuO)4Si:680.0H2O.By 3.74 g Ru/SiO2It is dispersed in water to form the suspension of 10wt%.By 2.0 g
C16TMAB is dissolved in 33.7 g distilled water, and 8.35 g HCl solutions (36wt%) are then added.30 minutes are stirred the mixture for, shape
At clear homogeneous solution.Ru/SiO is sequentially added into the solution2Suspension and 14.05 g (BuO)4Si.It is stirred using magnetic force
Device is mixed at room temperature with the speed stirring mixture 20h of 300-350r/min.Solid product is collected by filtration, is washed with water and ethyl alcohol
It washs for several times, it is then dry at 313 K in air.Product is calcined to 6 h in air at 823 K to remove and remaining have
Machine substance.
Use example: by 4 gained Ru/SiO of embodiment2@m-SiO2Catalyst with core-casing structure is applied in preparing cyclohexene from benzene added with hydrogen work
(reaction pressure: reaction temperature: 5.0 MPa 150 DEG C, react revolving speed: 1000 r/min, the body of benzene and water in reactant in skill
Product is than being 1:2, catalyst 1g, benzene 100ml, reaction time 1h), measure benzene conversion ratio 76.96%, cyclohexene selectivity
78.64.%。
Embodiment 5
The present embodiment is used to illustrate the preparation method of (Ru/MeOx)@m-MeOx core-shell structure bifunctional catalyst, including following step
It is rapid:
(1) Ru/SnO2Preparation: by feed molar match SnO2: RuCl3·3H2O=60:1, by 7.15 g SnO2At 100 DEG C
Baking oven in be dried overnight, and be dispersed in RuCl under ultrasonication3·3H2In O aqueous solution (0.2082 g, 300 mL), so
After be vigorously stirred 3h.By being centrifugated suspension obtained, it is washed with deionized until AgNO3Reagent is not detected
Cl-, 12 h are then dried at 60 DEG C in air circulation oven.Then, at 400 DEG C, by sample in 10% H2(H2/
N2=1:9, v/v) 3 h of middle reduction, the rate of heat addition is 5 DEG C of min-1, obtain SnO2The Ru particle of load；
(2) (Ru/SnO2)@m-SnO2Preparation: mole group of liquid phase feed become 1.0 CnTMAB:18.0 HCl:8.0
(BuO)4Sn:680.0H2O.By 3.74 g Ru/SnO2It is dispersed in water to form the suspension of 10wt%.By 2.0 g
C16TMAB is dissolved in 33.7 g distilled water, and 8.35 g HCl solutions (36wt%) are then added.30 minutes are stirred the mixture for, shape
At clear homogeneous solution.Ru/SnO is sequentially added into the solution2Suspension and 17.80 g (BuO)4Sn.It is stirred using magnetic force
Device is mixed at room temperature with 20 h of the speed stirring mixture of 300-350r/min.Solid product is collected by filtration, with water and ethyl alcohol
Washing is for several times, then dry at 313 K in air.It is remaining to remove that product is calcined to 6 h in air at 823 K
Organic substance.
Use example: by 5 gained Ru/SnO of embodiment2@m-SnO2Catalyst with core-casing structure is applied in preparing cyclohexene from benzene added with hydrogen work
(reaction pressure: reaction temperature: 5.0 MPa 150 DEG C, react revolving speed: 1000 r/min, the body of benzene and water in reactant in skill
Product is than being 1:2, catalyst 1g, benzene 100ml, reaction time 1h), measure benzene conversion ratio 63.48%, cyclohexene selectivity
75.23.%。
The active comparing result of the preparing cyclohexene from benzene added with hydrogen of 1 gained catalyst of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| The conversion ratio (%) of benzene | 94.60 | 93.49 | 89.94 | 76.96 | 63.48 |
| The selectivity (%) of cyclohexene | 81.32 | 82.96 | 79.58 | 78.94 | 75.23 |
In table 1:
Embodiment 1-5 shows very high conversion ratio and selectivity in benzene hydrogenation.
The above is only section Example of the invention, is not intended to limit the present invention in any form, and is appointed
What is to the above embodiments according to the technical essence of the invention any simply to repair without departing from technical solution of the present invention content
Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. the preparation method of one kind (Ru/MeOx)@m-MeOx core-shell structure bifunctional catalyst, which is characterized in that this method packet
Include following steps:
(1) preparation of Ru/MeOx: MeOx:RuCl is matched by feed molar3·3H2O=60 ~ 90:1, by MeOx at 60 ~ 100 DEG C
Baking oven in be dried overnight, and be dispersed in RuCl under ultrasonication3·3H2In O aqueous solution, 2 ~ 10 h are then vigorously stirred,
By being centrifugated suspension obtained, then washing, drying, reduction obtain Ru/MeOx particle；
(2) preparation of Ru/MeOx@m-MeOx: Ru/MeOx is dispersed in water to form suspending liquid A；Template is dissolved in distillation
In water, HCl solution is then added, stirs the mixture for 30 ~ 60 minutes, forms homogeneous solution B；Ru/ is sequentially added into solution B
MeOx suspending liquid A and (BuO)4Me is subsequently agitated for, and is filtered, and is washed, dry, calcining, to obtain Ru/MeOx@m-MeOx catalysis
Agent.
2. method according to claim 1, in step (1), MeOx:RuCl3·3H2O=60 ~ 80:1, the dry temperature
Degree is 50 ~ 80 DEG C, and the time is 10 ~ 12h；The volume group of reducing gas becomes H during described2: N2=1:8 ~ 15, reduction temperature are
350 ~ 450 DEG C, the time is 3 ~ 6 h.
3. method according to claim 1, in step (2), mole group of liquid phase feed becomes template: HCl:
(BuO)4Me:H2O=1.0:10 ~ 20:5.0 ~ 12.0:620.0 ~ 850.0.
4. method according to claim 1, in step (2), the mass fraction of Ru/MeOx water slurry be 6wt% ~
10wt%, the mass fraction of HCl solution are 32wt% ~ 38wt%.
5. method according to claim 1, in step (2), whipping temp is 20 ~ 30 DEG C, and mixing speed is 300 ~ 350
R/min, mixing time are 15 ~ 20 h.
6. method according to claim 1, in step (2), dry temperature is 313K ~ 365K, calcination temperature 773
~ 873K, calcination time are 4 ~ 10 h.
7. method according to claim 1, the MeOx is graphite oxide, is silica, titanium dioxide, two
One or more of tin oxide and zirconium oxide.
8. method according to claim 1, the template is ten alkyl trimethyl ammonium bromides, tetradecyl trimethyl
One or more of base ammonium bromide, cetyl trimethylammonium bromide.
9. method according to claim 1, (BuO)4Me is tetra-n-butyl titanate, four N-butyl of silicic acid, stannic acid
One or more of four N-butyl of four N-butyls and zirconic acid.
10. the catalyst that method according to claim 1 obtains can be used for the reaction of partial hydrogenation of benzene cyclohexene.
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Cited By (2)
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| CN110479259A (en) * | 2019-08-23 | 2019-11-22 | 福州大学 | It is a kind of using molybdenum oxide-zinc oxide-zirconia composite oxide as the support type Ru base catalyst of carrier |
| CN112871161A (en) * | 2021-02-20 | 2021-06-01 | 浙江工业大学上虞研究院有限公司 | Preparation method of catalyst for preparing cyclohexene by benzene selective hydrogenation |
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