CN106466614A - A kind of porous metal oxide coats the preparation method of ruthenium-based catalyst and its application of catalysis producing cyclohexene with benzene selective hydrogenation - Google Patents
A kind of porous metal oxide coats the preparation method of ruthenium-based catalyst and its application of catalysis producing cyclohexene with benzene selective hydrogenation Download PDFInfo
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- CN106466614A CN106466614A CN201610840463.8A CN201610840463A CN106466614A CN 106466614 A CN106466614 A CN 106466614A CN 201610840463 A CN201610840463 A CN 201610840463A CN 106466614 A CN106466614 A CN 106466614A
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- Prior art keywords
- ruthenium
- metal oxide
- benzene
- based catalyst
- oxide
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 102
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 40
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 13
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 13
- 238000005253 cladding Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000005464 sample preparation method Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 9
- 239000010410 layer Substances 0.000 abstract description 8
- 239000012752 auxiliary agent Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000010494 dissociation reaction Methods 0.000 abstract description 3
- 230000005593 dissociations Effects 0.000 abstract description 3
- 239000002345 surface coating layer Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 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 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000005574 cross-species transmission Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WNYDKEVRGDTCLJ-UHFFFAOYSA-N oxygen(2-) ruthenium(3+) zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4].[Ru+3] WNYDKEVRGDTCLJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JWXFFWOSZTYVQD-UHFFFAOYSA-N oxygen(2-) ruthenium(3+) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Ru+3] JWXFFWOSZTYVQD-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
- C07C2527/13—Platinum group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of be applied to benzene liquid phase selective and be hydrogenated with the porous metal oxide of cyclohexene reaction coat the preparation method of ruthenium-based catalyst.Method for preparing catalyst includes metal oxide supported ruthenium sample being obtained by impregnating the method reducing, and subsequently coats one layer of corresponding porous metal oxide in metal oxide supported ruthenium sample surfaces.This method gained ruthenium-based catalyst can be by the control in the aperture to surface coating layer, realize hydrogen molecule and enter duct contacting with active metal ruthenium in effective limited reactions thing benzene entrance duct while contact with ruthenium, thus realizing efficiently separating of metal dissociation hydrogen activity position and carrier hydrogenation activity position.This new catalyst can significantly improve the selectivity of benzene selective hydrogenation under conditions of need not adding auxiliary agent.
Description
Technical field
The invention belongs to catalyst preparation technical field is and in particular to one kind is applied to benzene liquid phase selective Hydrogenation hexamethylene
The porous metal oxide of alkene reaction coats the preparation method of ruthenium-based catalyst.
Background technology
Cyclohexene is a kind of important chemical intermediate, is widely used in medicine, pesticide, feed additive, polyester etc. fine
The production of chemicals.Traditional technique preparing cyclohexene mainly has alkyl halide dehalogenation, dehydration of cyclohexanol method and Brich reduction
Deng.But these methods have such problems as that high cost, seriously polluted, etching apparatus, side-product are many, do not meet sending out of Green Chemistry
Exhibition requires.And benzene selective is hydrogenated with cyclohexene, because its reaction raw materials is cheap and easy to get, reaction of atomic economy is strong and easy and simple to handle
The advantages of cause the extensive concern of researcher.
Why up to the present benzene selective hydrogenation cyclohexene be a worldwide technological puzzle, is primarily due to anti-
The cyclohexene generating during answering was easy to be hydrogenated to hexamethylene.Drinkard of du pont company in 1972 etc. uses
Ruthenium catalyst, adds the additives such as water miscible metal inorganic salt or metal carbonyl in aqueous phase system, cyclohexene
Yield reaches more than 30% first.The acquisition of this yield has indicated that benzene selective hydrogenation is prepared cyclohexene and possessed industrial applications
It is worth.Nylon -66 saltworks of Shen Ma group of China has introduced the technology of Asahi Chemical Industry within 1996, establishes the first benzene catalysis of China
Select the production line of hydrogenation cyclohexene so that cyclohexene can occur on market at home as a kind of raw material of industry.But
Japan grasps key technology and makes seriously to constrain the economic benefit of Chinese Enterprises limited by domestic cyclohexene expanding production and independently send out
Exhibition.For this reason, the research deeply developing ruthenium-based catalyst catalysis benzene selective hydrogenation synthesizing cyclohexene has highly important reality meaning
Justice.
At present, the research being hydrogenated with cyclohexene to ruthenium-based catalyst catalysis benzene selective is concentrated mainly on addition agent modified, golden
Belong to the aspect such as the regulation and control of ruthenium active sites and carrier regulation and control.CN105664931A discloses SiO2Cladding ruthenium-based catalyst, due to nanometer
Level SiO2 has Superhydrophilic, and the catalyst surface being suspended in aqueous phase can form one layer of delay moisture film, using benzene and cyclohexene
The difference of dissolving and scattering nature in being detained moisture film, the hexamethylene generating during stoping partial hydrogenation of benzene is adsorbed to again
There is deep hydrogenation to hexamethylene in catalyst surface.Add hydrophilic and the covering part hydrogenation that auxiliary agent can strengthen catalyst
Active site is thus effectively improve the selectivity of cyclohexene.But, can there is etching apparatus in the interpolation of auxiliary agent, pollution environment etc. is asked
Topic.In order to meet the demand for development of 21 century Green Chemistry, the preparation of efficient green benzene selective hydrogenation catalyst seems particularly heavy
Will.
Content of the invention
It is an object of the invention to provide the green high-efficient ruthenium-based catalytic that a class a operation reacts in producing cyclohexene with benzene selective hydrogenation
Agent and its general preparation method.
It is carrier that the present invention selects metal-oxide (as zirconium dioxide, ceria, titanium dioxide etc.), by infusion process
First prepare oxide carried metal Ru sample.Then, adjust its Surface Physical Chemistry property using alkali liquor, be allowed to suitable
PH value range interior energy by the method for sol-gel make its hydrolyze precursor surface formed clad, be simultaneously introduced pore creating material
Through follow-up calcination process metal oxide supported one layer of porous of metal Ru catalyst surface modification metal-oxide.These
Metal-oxide must have " Hydrogen spillover " effect, such as metal-oxide ceria, zirconium dioxide and titanium dioxide etc..Pass through
The metal-oxide aperture of surface modification is controlled, can hydrogen molecule realized enters duct and contact with metal Ru dissociateing activity
While hydrogen, effective limited reactions thing benzene is entered duct and is contacted with active metal ruthenium, thus realizing metal dissociation hydrogen activity position and load
The efficiently separating of body hydrogenation activity position.This new catalytic hydrogenation site has an excellent hydrophilic and to product hexamethylene
The weak active force of alkene, is more beneficial for the desorption of cyclohexene, has obvious action to improving its selectivity.
The concrete preparation process of the present invention is as follows：
(1) 0.1-1g metal oxide supported ruthenium sample, 0.1-1g pore creating material is taken to put into containing 50-100mL deionized water
Container in make A liquid；
(2) take 0.1-1g metal-oxide hydrolysis precursor to be dissolved in 5-20ml water and make B liquid；
(3) B liquid is slowly dropped in A liquid under the conditions of 50-100 DEG C, after completion of dropping, is that 0.1-1M alkali liquor is adjusted with concentration
Save solution ph between 7-10, after isothermal reaction 3-5h, centrifugal drying, then roasting, to remove pore creating material, forms and has spy
The pore passage structure of sizing, obtains porous metal oxide cladding ruthenium-based catalyst.
Wherein, described metal-oxide is zirconium dioxide, ceria or titanium dioxide；Before described metal-oxide hydrolysis
Body is basic zirconium chloride, six nitric hydrate ceriums or tetrabutyl titanate.
Described metal oxide supported ruthenium sample preparation methods comprise the steps：
A (), under the conditions of 0-50 DEG C, weighs 0.5-10g metal-oxide and is dissolved in 10-100ml deionized water, in magnetic force
The chloride hydrate ruthenium solution of the 1M of 1-10mL is added under conditions of stirring；
B () alkali liquor of 0.1-1M is added dropwise in the suspension that step (a) obtains under conditions of magnetic agitation, adjust
Section pH value is 6-9, continues magnetic agitation 60-240min；
C product deionized water and absolute ethanol washing centrifugation that step (b) is obtained by (), until examined with silver nitrate solution
Do not measure till containing chloride ion in centrifugal liquid, 12-24h is dried at 60-120 DEG C, grind, and in hydrogen volume concentration be
1-5h is reduced at 100-500 DEG C, you can obtain metal oxide supported ruthenium sample in the hydrogen-nitrogen mixture gas of 0.05-1.
The aperture of wherein said porous metal oxide is less than the kinetics radius of benzene.
In step (3), baking temperature is 60-120 DEG C, and drying time is 12-24h.
Sintering temperature in step (3) is 350-550 DEG C, and heating rate is 2-5 DEG C/min, heats up and reaches assigned temperature guarantor
Lower the temperature after warm 3-5h.
Wherein, described alkali liquor is sodium hydroxide, ammonia or sodium carbonate liquor；Pore creating material is Tetradecyl Trimethyl Ammonium Bromide
Or cetyl trimethylammonium bromide.
The invention still further relates to porous metal oxide coats the application of ruthenium-based catalyst.The porous metal oxide of the present invention
Cladding ruthenium-based catalyst can be used for the reaction of producing cyclohexene with benzene selective hydrogenation.
Porous metal oxide cladding ruthenium-based catalyst catalysis benzene liquid phase selective hydrogenation cyclohexene with present invention preparation
React, concrete reaction condition is：Weigh 0.05-0.2g catalyst, add 10- in 100-200mL high pressure batch reactor
40ml benzene and 20-80ml deionized water；After check device sealing, use highly purified H2Air in displacement kettle 3-5 time；Displacement
Finish rear sealed reactor, under 100-400r/min speed of agitator, reactor is heated to 130-160 DEG C, is passed through H2To kettle
Interior pressure is 3.0-5.0MPa, then improves rotating speed to 700-1200r/min, starts to react timing, gathers different in course of reaction
The reactant of period carries out gas chromatographic analysiss.
It is an advantage of the current invention that：Coat ruthenio loaded catalyst, this preparation side for preparing Multimetal oxide
Method has universality.This method gained ruthenium-based catalyst can realize hydrogen by the control in the aperture to surface coating layer
Molecule is entered effective limited reactions thing benzene entrance duct while duct is contacted with ruthenium and is contacted with active metal ruthenium, thus realizing gold
Belong to dissociation hydrogen activity position and the efficiently separating of carrier hydrogenation activity position.Additionally, by oxide carried metal Ru sample surfaces
Modify the suitable porous zirconium dioxide in one layer of aperture or ceria again, so can utilize Hydrogen spillover hydrogenation mechanism catalysis completely
Benzene hydrogenation, it is to avoid the cyclohexene that benzene is hydrogenated on traditional metal Ru surface is because of itself and metal Ru active sites stronger effects
Power and easy mistake is hydrogenated to hexamethylene.The ruthenio of the zirconium dioxide, ceria or coated by titanium dioxide of the method preparation is urged
Agent process is simple, favorable reproducibility, are suitable to industrialized production.And the zirconium dioxide ruthenium-based catalytic being coated by porous zirconium dioxide
Agent, the ceria ruthenium-based catalyst being coated by porous silica cerium and the titanium dioxide ruthenio being coated by poriferous titanium dioxide
Catalyst need not add auxiliary agent to be remarkably improved the selectivity of benzene selective hydrogenation during catalysis benzene selective hydrogenation,
150 DEG C, the conversion ratio respectively reaching benzene under 5.0MPa is 60%, 66% and 98.1%；The selection of corresponding target product cyclohexene
Property be respectively be 46%, 53% and 76.6%.Reaction green, reaction-ure conversion-age height, the selectivity of product and catalyst stabilization
Property is good.
Brief description
Fig. 1 is the TEM image in zirconia-supported one layer of porous zirconium dioxide of ruthenium Surface coating of embodiment 1 preparation.
Fig. 2 is the TEM image in CeO 2 supporting one layer of porous silica cerium of ruthenium Surface coating of embodiment 1 preparation.
Fig. 3 is the TEM image in titanium dichloride load one layer of poriferous titanium dioxide of ruthenium Surface coating of embodiment 1 preparation.
Specific embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1
Under the conditions of 25 DEG C, weigh 2g zirconium dioxide, ceria or titanium dioxide and be dissolved in 100ml deionized water for carrier
In, add under conditions of magnetic agitation volume be 1.98ml concentration be 1M chloride hydrate ruthenium solution, be then 0.2M with concentration
Ammonia is added dropwise in above-mentioned suspension under conditions of magnetic agitation, adjusts pH value to 7.0, continues magnetic agitation 240min；
Deionized water and absolute ethanol washing centrifugation, until do not measured in centrifugal liquid containing till chloride ion with silver nitrate solution inspection.
Then obtained Centrifuge A sample takes out after 12h being dried at 60 DEG C, is ground to uniform fine powder, and the volumetric concentration with hydrogen
Hydrogen nitrogen mixed gas for 0.1 reduce 3h at 400 DEG C, you can obtain oxide carried ruthenium sample.
Further, above-mentioned oxide carried metal Ru sample surfaces are coated one layer of porous metal oxide dioxy by again
Change zirconium, ceria or titanium dioxide, zirconium dioxide corresponding cladding carrier zirconium dioxide, ceria corresponding cladding carrier dioxy
Change cerium, titanium dioxide corresponding cladding carrier titanium dioxide.The process relating generally to has：Take 1g zirconium dioxide (ceria, dioxy
Change titanium) load ruthenium sample and 1g pore creating material Tetradecyl Trimethyl Ammonium Bromide put in the container containing 100ml deionized water system
Become A liquid.Take 1g basic zirconium chloride (six nitric hydrate ceriums, tetrabutyl titanate) to be dissolved in 20ml water and make B liquid.By B liquid in 80 DEG C of bars
It is slowly dropped under part in mix homogeneously A liquid.After completion of dropping, it is that 0.2M ammonia adjusts solution ph to 10 with concentration, constant temperature is anti-
After answering 5h, centrifugal drying.Products therefrom takes out after first 12h being dried at 60 DEG C, then again in 400 DEG C of roastings to remove pore-creating
Agent, forms the pore passage structure with particular size.Roasting condition：2-5 DEG C/min heating rate, after reaching assigned temperature insulation 3h
Cooling.
The ruthenium-based catalyst catalysis benzene of porous zirconium dioxide, ceria or the coated by titanium dioxide prepared in aforementioned manners
Liquid phase selective hydrogenation cyclohexene reacts, and reaction condition is：Weigh 0.1g catalyst, add in 100ml high pressure batch reactor
Enter 10ml benzene and 20ml deionized water.After check device sealing, use highly purified H2Air in displacement kettle 3 times.Replace
Sealed reactor after finishing, under 500r/min speed of agitator, reactor is heated to 150 DEG C of temperature, is passed through H2The pressure to kettle
For 5.0MPa, then improve rotating speed (1000r/min), start to react timing, the reactant gathering different periods in course of reaction enters
Circulation of qi promoting analysis of hplc.
Using Shimadzu Corporation's gas chromatogram, quantitative analyses are carried out to product, after tested, porous zirconium dioxide cladding
After zirconium dioxide ruthenium-based catalyst hydrogenation reaction carries out 120min, the conversion ratio of benzene reaches 60%, the choosing of target product cyclohexene
Selecting property is 46%；After the ceria ruthenium-based catalyst hydrogenation reaction of porous silica cerium cladding carries out 180min, the conversion of benzene
Rate reaches 66%, and the selectivity of target product cyclohexene is 53%；The titanium dioxide ruthenium-based catalyst of poriferous titanium dioxide cladding
After hydrogenation reaction carries out 210min, the conversion ratio of benzene is up to 98.1%, and the selectivity of target product cyclohexene is 76.6%.
Claims (8)
1. a kind of porous metal oxide coat ruthenium-based catalyst preparation method it is characterised in that：In metal-oxide ruthenio
Catalyst surface coats one layer of corresponding porous metal oxide, and cladding process comprises the steps：
(1) 0.1-1g metal oxide supported ruthenium sample, 0.1-1g pore creating material is taken to put into the appearance containing 50-100mL deionized water
A liquid is made in device；
(2) take 0.1-1g metal-oxide hydrolysis precursor to be dissolved in 5-20ml water and make B liquid；
(3) B liquid is slowly dropped in A liquid under the conditions of 50-100 DEG C, after completion of dropping, is that the regulation of 0.1-1M alkali liquor is molten with concentration
Liquid pH value between 7-10, after isothermal reaction 3-5h, centrifugal drying, then roasting to remove pore creating material, formed have specific big
Little pore passage structure, obtains porous metal oxide cladding ruthenium-based catalyst；
Wherein, described metal-oxide is zirconium dioxide, ceria or titanium dioxide；Described metal-oxide hydrolysis precursor is
Basic zirconium chloride, six nitric hydrate ceriums or tetrabutyl titanate.
2. the method for claim 1 wherein that described metal oxide supported ruthenium sample preparation methods comprise the steps：
A (), under the conditions of 0-50 DEG C, weighs 0.5-10g metal-oxide and is dissolved in 10-100ml deionized water, in magnetic agitation
Under conditions of add 1-10mL 1M chloride hydrate ruthenium solution；
B () alkali liquor of 0.1-1M is added dropwise in the suspension that step (a) obtains under conditions of magnetic agitation, adjust pH
It is worth for 6-9, continuation magnetic agitation 60-240min；
C product deionized water and absolute ethanol washing centrifugation that step (b) is obtained by (), until detected not with silver nitrate solution
Go out till containing chloride ion in centrifugal liquid, 12-24h is dried at 60-120 DEG C, grind, and be 0.05-1 in hydrogen volume concentration
Hydrogen-nitrogen mixture gas at 100-500 DEG C reduce 1-5h, you can metal oxide supported ruthenium sample.
3. the method for claim 1 or 2, the aperture of wherein said porous metal oxide is less than the kinetics radius of benzene.
4. in the method for claim 1 or 2, wherein step (3), baking temperature is 60-120 DEG C, and drying time is 12-24h.
5. the sintering temperature in the method for claim 1 or 2, wherein step (3) be 350-550 DEG C, heating rate be 2-5 DEG C/
Min, heats up and lowers the temperature after reaching assigned temperature insulation 3-5h.
6. the method for claim 1 or 2, wherein said alkali liquor is sodium hydroxide, ammonia or sodium carbonate liquor.
7. the method for claim 1 or 2, wherein said pore creating material is Tetradecyl Trimethyl Ammonium Bromide or cetyl trimethyl
Ammonium bromide.
8. the porous metal oxide that a kind of claim 1-7 any one methods described obtains coats the application of ruthenium-based catalyst,
It is characterized in that, described catalyst is used for producing cyclohexene with benzene selective hydrogenation reaction.
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| CN109794236A (en) * | 2019-01-26 | 2019-05-24 | 福州大学 | A kind of preparation of the nucleocapsid catalyst of efficient prepared from benzene and hydrogen for cyclohexene |
| CN112915998A (en) * | 2021-02-22 | 2021-06-08 | 浙江工业大学上虞研究院有限公司 | Preparation method of composite ruthenium catalyst |
| CN115920886A (en) * | 2023-02-23 | 2023-04-07 | 北京化工大学 | Palladium-loaded tungsten oxide-montmorillonite bifunctional catalyst and application thereof in preparation of cyclohexylbenzene by catalytic benzene hydroalkylation |
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