CN105664931A - Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and modification method of Ru-based catalyst - Google Patents
Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and modification method of Ru-based catalyst Download PDFInfo
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- CN105664931A CN105664931A CN201610055616.8A CN201610055616A CN105664931A CN 105664931 A CN105664931 A CN 105664931A CN 201610055616 A CN201610055616 A CN 201610055616A CN 105664931 A CN105664931 A CN 105664931A
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- benzene
- based catalyst
- cyclohexene
- partial hydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 69
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title abstract description 129
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title abstract description 85
- 238000002715 modification method Methods 0.000 title abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 41
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 41
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims description 23
- OSKSAMGBRKRQOZ-UHFFFAOYSA-N benzene cyclohexene Chemical compound C1CCC=CC1.C1CCC=CC1.C1=CC=CC=C1 OSKSAMGBRKRQOZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 abstract 5
- 239000002245 particle Substances 0.000 abstract 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000003756 stirring Methods 0.000 description 15
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000005253 cladding Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 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 3
- 230000008569 process Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ROXGIDGASNKPLW-UHFFFAOYSA-N benzene;cyclohexene Chemical class C1CCC=CC1.C1=CC=CC=C1 ROXGIDGASNKPLW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 hexamethylene Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/60—Platinum group metals with zinc, cadmium or mercury
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Catalysts (AREA)
Abstract
The invention relates to a Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and a modification method of the Ru-based catalyst. The Ru-based catalyst comprises Ru-based particles and a SiO2 layer, wherein the Ru-based particles are coated with the SiO2 layer, a core-shell catalyst is formed, and the thickness of the SiO2 layer is 0.5-2 nm; the Ru-based particles are the Ru-based catalyst. With the adoption of the Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and the modification method of the Ru-based catalyst, the condition that cyclohexene generated in the partial hydrogenation process of benzene is adsorbed to the surface of the catalyst again and is subjected to deep hydrogenation to generate cyclohexane is prevented on the basis of the difference of dissolution and diffusion properties of benzene and cyclohexene in a retained water membrane, the activity of the Ru-based catalyst before coated with SiO2 and the activity of the Ru-based catalyst after coated with SiO2 under the same hydrogenation condition are not remarkably influenced, the yield of a target product cyclohexene can be increased by 15%-20% or higher, and the Ru-based catalyst has a wider application range.
Description
Technical field
The present invention relates to chemical field, particularly relate to chemical catalyst field, specifically refer to a kind of ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene and method of modifying thereof.
Background technology
Cyclohexene is important industrial chemicals and intermediate, can be used for the important organic productss such as synthetic lysine, Hexalin, Ketohexamethylene. The main path obtaining cyclohexene is chemosynthesis. Partial hydrogenation of benzene, with the benzene of industrial easy acquisition for raw material, obtains cyclohexene by partial hydrogenation, has that equipment investment is few, safety and stability, carbon yield high and the advantage such as environmental protection and energy saving. Preparing cyclohexene from benzene added with hydrogen mainly has complex catalysis method, gas-phase catalysis and liquid catalytic. The catalytic hydrogenation method wherein operating in aqueous phase, organic facies, solid catalyst phase and hydrogen these four special phase catalyst system and catalyzings mutually takes the lead in realizing industrialization in Japan in 1989, constitutes caprolactam industrial chain greenization and the important step of atom economy optimization.
From thermodynamics, benzene hydrogenation generates the Gibbs free (-23kJ.mol of cyclohexene-1) much smaller than the Gibbs free (-98kJ.mol generating hexamethylene-1), it is difficult to during benzene hydrogenation rest on the cyclohexene stage. From aerodynamic point, on phenyl ring, the stability of big π key is higher than the carbon-carbon double bond of cyclohexene, and cyclohexene is more easy to generation hydrogenation reaction than benzene. Select suitable catalyst and reaction system that the selectivity improving cyclohexene is extremely important.
Academia is concentrated mainly on three aspects for catalyst based modified of partial hydrogenation of benzene Ru: 1) adulterate at Ru metallic surface, doped chemical covers the nonmetalloid B of transition metal (such as Cu, Zn, Mn etc.) and electron deficiency, it is intended to change benzene, cyclohexene and hexamethylene at the absorption of catalyst surface and hydrogenation intrinsic kinetics by effects such as electron transfers; 2) hydrophilic support such as SiO is selected2And ZrO2Deng, the hydrophilic (referring to Fig. 1) that strengthening support type Ru is catalyst based; 3) Organic substance such as methanol is introduced, it is desirable to improved the hydrophilic of catalyst surface further in the absorption of catalyst surface by these small-molecule substances.
Early stage, China was when Introduced from Japan Asahi Chemical Industry partial hydrogenation of benzene cyclohexene technique, and the patent of catalyst rests in Japanese side's hands completely.After calendar year 2001 Zhengzhou University's expansion correlational study, situation has had great improvement. According to bibliographical information, on the Ru that selectivity is the highest is catalyst based, the yield of cyclohexene can to 60%. Even but having to it is noted that most of high yield data is also difficult to obtain repeated authentication in the lab. The highly desirable exploitation of industrial quarters is a kind of simple, with low cost, effective and reproducible to the catalyst based method being modified of Ru.
Summary of the invention
It is an object of the invention to the shortcoming overcoming above-mentioned prior art, it is provided that one is capable of coated Si O under identical hydroconversion condition2Before and after the catalyst based activity of Ru be not subject to a significant impact and the yield of target product cyclohexene can increase by more than 15～20% the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene and method of modifying thereof.
To achieve these goals, the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene of the present invention and method of modifying thereof have following composition:
This is to the ruthenium-based catalyst of partial hydrogenation of benzene cyclohexene and method of modifying thereof, and it is mainly characterized by, and described ruthenium-based catalyst includes:
Ruthenio Ru granule and SiO2Layer, described SiO2Layer is coated on outside described ruthenio Ru granule, forms nucleocapsid catalyst, described SiO2The thickness of layer is 0.5～2nm; Described ruthenio Ru granule is ruthenio Ru catalyst.
Preferably, described ruthenio Ru catalyst is pure Ru or Ru and the RuX alloying pellet of other element formation.
It is highly preferred that X includes B, Zn or Cu in described RuX alloying pellet.
Most preferably, described ruthenium-based catalyst is used for partial hydrogenation of benzene cyclohexene.
The method of modifying of a kind of described ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene, it is mainly characterized by, and described method of modifying comprises the steps:
(1) the ruthenio Ru catalyst that preparation is described;
(2) in the ruthenio Ru catalyst prepared, well-mixed tetraethyl orthosilicate and ammonia, magnetic agitation are added.
Preferably, described step (2) particularly as follows:
The ruthenio Ru catalyst prepared adds well-mixed tetraethyl orthosilicate and ammonia, washing with alcohol 2 times after magnetic agitation 2h.
Most preferably, described step (2) also needs add dehydrated alcohol and distilled water, add after being sufficiently mixed with tetraethyl orthosilicate and ammonia in described ruthenio Ru catalyst.
Have employed the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene in this invention and method of modifying thereof, principle, nanoscale SiO2Cladding be applicable to catalyst based modified of the Ru of overwhelming majority partial hydrogenation of benzene cyclohexenes. Due to nanoscale SiO2There is Superhydrophilic, be suspended in the RuSiO in aqueous phase2Or RuX(X=B, Cu, Zn, Mn ...)SiO2Nucleocapsid catalyst surface can form one layer and be detained moisture film. Utilize benzene and cyclohexene being detained in moisture film to dissolve and the difference of scattering nature, stop the cyclohexene generated in partial hydrogenation of benzene process to be again adsorbed to catalyst surface generation deep hydrogenation to hexamethylene. In traditional partial hydrogenation of benzene four phase catalyst system and catalyzing, coated Si O under identical hydroconversion condition2Activity catalyst based for front and back Ru is not subject to a significant impact, and the yield of target product cyclohexene can increase by more than 15～20%, and final cyclohexene stable yield is 35～42%.
Accompanying drawing explanation
Fig. 1 is that conventional load type Ru is catalyst based and SiO2Cladded type Ru base nucleocapsid catalyst schematic diagram.
Fig. 2 is the RuSiO of the present invention2Or RuX(X=B, Cu, Zn, Mn ...)SiO2Nucleocapsid catalyst partial schematic diagram.
Fig. 3 is the RuSiO of the present invention2The FTIR of catalyst characterizes data.
Fig. 4 is the RuSiO of the present invention2The XRD of catalyst characterizes data.
Fig. 5 is the RuSiO of the present invention2The TEM of catalyst characterizes collection of illustrative plates.
Fig. 6 is the Ru granule bag SiO of the present invention2Impact on partial hydrogenation of benzene cyclohexene yield.
Fig. 7 is the RuZn granule bag SiO of the present invention2Impact on partial hydrogenation of benzene cyclohexene yield.
Fig. 8 is the RuB granule bag SiO of the present invention2Impact on partial hydrogenation of benzene cyclohexene yield.
Accompanying drawing explanation
1SiO2Cladded type
2Ru base core
Detailed description of the invention
In order to more clearly describe the technology contents of the present invention, conduct further description below in conjunction with specific embodiment.
Using for reference and generally acknowledge research conclusion at present, the hydrophilic namely improving the catalyst based surface of Ru is conducive to improving the yield of cyclohexene. Being different from the catalyst based framework of conventional load type Ru, inventor herein proposes at the super hydrophilic nanoscale SiO of the catalyst based Surface coating of Ru one layer2(as shown in Figure 1). SiO2Crystal itself has hydrophilic, its initial stage hydrophilic angle≤10 °, continues hydrophilic angle≤20 °. As nanoscale SiO2After being coated on the catalyst based surface of Ru, SiO2There is substantial amounts of unsaturated residual bond and the hydroxyl of different bond styles in surface, deviate from stable silica structure because surface is oxygen debt and have Superhydrophilic (referring to Fig. 2). When being coated with SiO2Ru catalyst based be suspended in partial hydrogenation of benzene system aqueous phase time, hydrone and SiO2The effect of the various residual bond in surface makes catalyst surface form stable delay moisture film. Relative to the aqueous phase of high turbulence, the formation being detained moisture film is proved and can again be adsorbed to catalyst surface generation deep hydrogenation by the more effective cyclohexene preventing from having generated.
Make SiO2Layer can play intended effect, it is necessary to its structural parameters are made constraint. Specifically, SiO2The thickness of layer should control in the reasonable scope. SiO2If clad is blocked up, reaction raw materials benzene cannot diffuse through SiO2Layer arrives hydrogenation activity substrate and carries out hydrogenation reaction. Now the hydrogenation activity of catalyst sharply declines or directly translates into inactive. SiO2If clad is excessively thin, the delay moisture film of adequate thickness just cannot be formed at hydrogenation activity substrate surface. The cyclohexene that now partial hydrogenation generates remains able to diffuse to catalyst substrate surface from aqueous phase smoothly and deep hydrogenation occurs, and the selectivity of cyclohexene and yield are almost without improvement. According to optimal screening, the catalyst based surface SiO of Ru2The THICKNESS CONTROL of layer is advisable at 0.5～2nm.
Nanoscale SiO2Before and after cladding, the catalyst based Active sites of Ru does not have any change, therefore the hydrogenation activity of partial hydrogenation of benzene initial stage catalyst and selectivity usually not significant change to cyclohexene. When hydrogenation enters middle and late stage, cyclohexene concentration in reaction system occupies advantage gradually relative to benzene. If Ru is catalyst based does not have coated Si O2, laboratory observation is it appeared that namely the yield of cyclohexene sharply declines after peaking. It has been coated with SiO when Ru is catalyst based2After, the existence being detained moisture film can effectively prevent cyclohexene adsorbing again on the catalyst based surface of Ru again. Correspondingly, the deep hydrogenation of cyclohexene is subject to effective suppression. It is experimentally confirmed that SiO2The contribution improved for cyclohexene selectivity and yield after cladding is mainly reflected in the middle and late stage of hydrogenation.
The case study on implementation being exemplified below simply compares various Ru substrate coated Si O under fixing hydroconversion condition2The process conditions of partial hydrogenation of benzene are not deliberately optimized by the hydrogenation effect of front and back.It is contemplated that higher cyclohexene yield and selectivity will can be being obtained after process optimization.
Embodiment 1:
RuSiO2The preparation of nucleocapsid catalyst
By a certain amount of RuCl3·3H2O is dissolved in 60ml distilled water, is stirred vigorously the NaOH solution of lower addition 15%, stands sucking filtration after fully reaction. The distillation washing 3 times of gained black solid, then wash 3 times by the NaOH solution of 5%, it is then dispersed in the NaOH solution of 5% and is transferred in autoclave. Under 5MPa hydrogen partial pressure, stir speed (S.S.) 800rpm, it is warming up to 150 DEG C of reduction 3h obtains Ru granule. In the eggplant-shape bottle of 250ml, add 40ml dehydrated alcohol, 5ml distilled water, a certain amount of tetraethyl orthosilicate and 200ul ammonia, after being sufficiently mixed, add Ru granule. After magnetic agitation 2h, washing with alcohol twice again, obtains RuSiO2Catalyst. The thickness of surface silicon layer is regulated by changing the amount of tetraethyl orthosilicate.
RuSiO2The physical characterization of nucleocapsid catalyst
RuSiO2The FTIR characterization result of catalyst is as shown in Figure 3. 1099cm-1Neighbouring strong and wide absorption band is Si-O-Si antisymmetric stretching vibration, 796cm-1、474cm-1The peak at place is Si-O key symmetrical stretching vibration peak, 3455cm-1The broad peak at place is constitution water-OH antisymmetric stretching vibration peak, 1635cm-1Neighbouring peak is the H-O-H bending vibration peak of water, 967cm-1The peak shoulder at place belongs to the bending vibration absworption peak of Si-OH. The appearance at above-mentioned infrared signature peak, it was shown that Ru core surface exists SiO2Silicon layer.
RuSiO2The XRD characterization result of catalyst is as shown in Figure 3. Being 38.7 ° in 2theta value, the position of 43.9 ° and 69.3 ° occurs in that the characteristic peak of the six close heap lattice structure Ru of side. Meanwhile, SiO2Crystal is at 20.9 °, and 26.6 °, 36.5 ° etc. due characteristic peaks are observed. In conjunction with data shown in Fig. 4, it is possible to infer, SiO2It is highly dispersed in Ru core surface.
Ru nucleocapsid SiO2The TEM characterization result of catalyst is as shown in Figure 5. From collection of illustrative plates, the main activity phase Ru of catalyst is actually the aggregate of a large amount of Ru granule. The yardstick of granule is nanoscale, and impersonal language of reuniting is up to submicron order. The SiO that contrast is relatively low can be significantly observed on the surface of Ru granule2The existence of clad. The thickness of clad is less than 3 nanometers.
RuSiO2The hydrogenation of nucleocapsid catalyst characterizes
Take 1gRuSiO2Or the quite Ru catalyst of active component quality, 17.25gZnSO4·7H2O and 100ml water is placed in autoclave. 140 DEG C of pretreatment 12h it are warming up to when 5MPa hydrogen partial pressure and stir speed (S.S.) 600rpm. After pretreatment, add 50ml benzene feedstock and carry out partial hydrogenation of benzene reaction. Reaction condition is 150 DEG C, H2Dividing potential drop 5MPa and stir speed (S.S.) 1000rpm. Regulating cooling coil current in course of reaction and be precisely controlled temperature, reaction stops hydrogen supply immediately and closes stirring and heating after terminating, strengthen cooling coil current and lower the temperature rapidly. Wait that reactor opens kettle cover after being cooled to room temperature, take a small amount of organic facies and be analyzed. Experimental result is as shown in Figure 6. SiO2Before cladding, when adopting pure Ru granule as partial hydrogenation of benzene catalyst. Can obtaining, during reaction 15min, the cyclohexene that the highest yield is 23%, the conversion ratio of benzene has reached 82%. SiO2After cladding, adopt RuSiO2As partial hydrogenation of benzene catalyst. Can obtaining, during reaction 15min, the cyclohexene that the highest yield is 41%, the conversion ratio of benzene has reached 75%.
Embodiment 2:
RuZnSiO2The preparation of nucleocapsid catalyst
Weigh the RuCl of 1.66g3·3H2O joins 150ml distilled water and is configured to solution. The KOH weighing 10.08g is dissolved in 100ml deionized water, moves in the there-necked flask being positioned in water bath with thermostatic control, opens stirring.Water bath with thermostatic control is warmed up to 80 DEG C, with the RuCl that the speed of 3ml/min will configure3Solution adds there-necked flask. After adding, at 80 DEG C, constant temperature stirring 1h then turns off stirring, natural cooling after continuation maintenance 80 DEG C of about 1h of constant temperature. Precipitum is washed with distilled water to neutrality, in company with the ZnSO of 50ml benzene, 100ml distilled water and 20g4·7H2O adds autoclave. RuZn alloying pellet is obtained subsequently at 180 DEG C, hydrogen partial pressure 5.0MPa and stir speed (S.S.) 1000rpm condition reduction 8h. In the eggplant-shape bottle of 250ml, add 40ml dehydrated alcohol, 5ml distilled water, a certain amount of tetraethyl orthosilicate and 200ul ammonia, after being sufficiently mixed, add RuZn granule. After magnetic agitation 2h, washing with alcohol twice again, obtains RuZnSiO2Catalyst. The thickness of surface silicon layer is regulated by changing the amount of tetraethyl orthosilicate. According to TEM result, RuZnSiO2The SiO on nucleocapsid catalyst top layer2Thickness is 1.5nm.
RuZnSiO2The hydrogenation of nucleocapsid catalyst characterizes
Take 1gRuZnSiO2Or the quite RuZn catalyst of active component quality, 17.25gZnSO4·7H2O and 100ml water is placed in autoclave. 140 DEG C of pretreatment 12h it are warming up to when 5MPa hydrogen partial pressure and stir speed (S.S.) 600rpm. After pretreatment, add 50ml benzene feedstock and carry out partial hydrogenation of benzene reaction. Reaction condition is 150 DEG C, H2Dividing potential drop 5MPa and stir speed (S.S.) 1000rpm. Regulating cooling coil current in course of reaction and be precisely controlled temperature, reaction stops hydrogen supply immediately and closes stirring and heating after terminating, strengthen cooling coil current and lower the temperature rapidly. Wait that reactor opens kettle cover after being cooled to room temperature, take a small amount of organic facies and be analyzed. Experimental result is as shown in Figure 7. SiO2Before cladding, when adopting RuZn alloy as partial hydrogenation of benzene catalyst. Can obtaining, during reaction 20min, the cyclohexene that the highest yield is 25%, the conversion ratio of benzene has reached 74%. SiO2After cladding, adopt RuZnSiO2As partial hydrogenation of benzene catalyst. Can obtaining, during reaction 25min, the cyclohexene that the highest yield is 38%, the conversion ratio of benzene has reached 72%.
Embodiment 3:
RuBSiO2The preparation of nucleocapsid catalyst
By the RuC1 of 50mL0.05mol/L3With the NaBH of 25mL0.5mol/L4Dropwise reduce. The complete continuation that reduce stirs 10min. Standing, filtration, distilled water obtain RuB granule after being washed till neutrality. In the eggplant-shape bottle of 250ml, add 40ml dehydrated alcohol, 5ml distilled water, a certain amount of tetraethyl orthosilicate and 200ul ammonia, after being sufficiently mixed, add RuB granule. After magnetic agitation 2h, washing with alcohol twice again, obtains RuSiO2Catalyst. The thickness of surface silicon layer is regulated by changing the amount of tetraethyl orthosilicate. According to TEM result, RuBSiO2The SiO on nucleocapsid catalyst top layer2Thickness is 1.0nm.
RuBSiO2The hydrogenation of catalyst characterizes
Take 1gRuBSiO2Or the quite RuB catalyst of active component quality, 17.25gZnSO4·7H2O and 100ml water is placed in autoclave. 140 DEG C of pretreatment 12h it are warming up to when 5MPa hydrogen partial pressure and stir speed (S.S.) 600rpm. After pretreatment, add 50ml benzene feedstock and carry out partial hydrogenation of benzene reaction. Reaction condition is 150 DEG C, H2Dividing potential drop 5MPa and stir speed (S.S.) 1000rpm. Regulating cooling coil current in course of reaction and be precisely controlled temperature, reaction stops hydrogen supply immediately and closes stirring and heating after terminating, strengthen cooling coil current and lower the temperature rapidly. Wait that reactor opens kettle cover after being cooled to room temperature, take a small amount of organic facies and be analyzed.Experimental result is as shown in Figure 8. SiO2Before cladding, when adopting RuB alloy as partial hydrogenation of benzene catalyst. Can obtaining, during reaction 10min, the cyclohexene that the highest yield is 29%, the conversion ratio of benzene has reached 68%. SiO2After cladding, adopt RuBSiO2As partial hydrogenation of benzene catalyst. Can obtaining, during reaction 15min, the cyclohexene that the highest yield is 39%, the conversion ratio of benzene has reached 74%.
Have employed the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene in this invention and method of modifying thereof, principle, nanoscale SiO2Cladding be applicable to catalyst based modified of the Ru of overwhelming majority partial hydrogenation of benzene cyclohexenes. Due to nanoscale SiO2There is Superhydrophilic, be suspended in the RuSiO in aqueous phase2Or RuX(X=B, Cu, Zn, Mn ...)SiO2Nucleocapsid catalyst surface can form one layer and be detained moisture film. Utilize benzene and cyclohexene being detained in moisture film to dissolve and the difference of scattering nature, stop the cyclohexene generated in partial hydrogenation of benzene process to be again adsorbed to catalyst surface generation deep hydrogenation to hexamethylene. In traditional partial hydrogenation of benzene four phase catalyst system and catalyzing, coated Si O under identical hydroconversion condition2Activity catalyst based for front and back Ru is not subject to a significant impact, and the yield of target product cyclohexene can increase by more than 15～20%, and final cyclohexene stable yield is 35～42%.
In this description, the present invention is described with reference to its specific embodiment. But it is clear that still may be made that various amendment and conversion are without departing from the spirit and scope of the present invention. Therefore, specification and drawings is regarded in an illustrative, rather than a restrictive.
Claims (7)
1. the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene, it is characterised in that described ruthenium-based catalyst includes:
Ruthenio Ru granule and SiO2Layer, described SiO2Layer is coated on outside described ruthenio Ru granule, forms nucleocapsid catalyst, described SiO2The thickness of layer is 0.5～2nm; Described ruthenio Ru granule is ruthenio Ru catalyst.
2. the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene according to claim 1, it is characterised in that described ruthenio Ru catalyst is pure Ru or Ru and the RuX alloying pellet of other element formation.
3. the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene according to claim 1, it is characterised in that in described RuX alloying pellet, X includes B, Zn or Cu.
4. the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene according to any one of claims 1 to 3, it is characterised in that described ruthenium-based catalyst is used for partial hydrogenation of benzene cyclohexene.
5. the method for modifying of the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene according to claim 1, it is characterised in that described method of modifying comprises the steps:
(1) the ruthenio Ru catalyst that preparation is described;
(2) in the ruthenio Ru catalyst prepared, well-mixed tetraethyl orthosilicate and ammonia, magnetic agitation are added.
6. the method for modifying of the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene according to claim 4, it is characterised in that described step (2) particularly as follows:
The ruthenio Ru catalyst prepared adds well-mixed tetraethyl orthosilicate and ammonia, washing with alcohol 2 times after magnetic agitation 2h.
7. the method for modifying of the ruthenium-based catalyst to partial hydrogenation of benzene cyclohexene according to claim 5, it is characterized in that, described step (2) also needs add dehydrated alcohol and distilled water, add after being sufficiently mixed with tetraethyl orthosilicate and ammonia in described ruthenio Ru catalyst.
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| CN109433201A (en) * | 2018-12-10 | 2019-03-08 | 郑州师范学院 | Producing cyclohexene with benzene selective hydrogenation Ru@Y2O3Catalyst and its preparation method and application |
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