CN117942978A - Hydrogenolysis catalyst, preparation method and application thereof, and method for preparing isopropylbenzene from alpha, alpha-dimethylbenzyl alcohol - Google Patents
Hydrogenolysis catalyst, preparation method and application thereof, and method for preparing isopropylbenzene from alpha, alpha-dimethylbenzyl alcohol Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 25
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 24
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- 238000001035 drying Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
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- 239000002994 raw material Substances 0.000 claims description 10
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- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
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- 238000005406 washing Methods 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
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- 229910052721 tungsten Inorganic materials 0.000 abstract description 12
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- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
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- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of catalysts, in particular to a hydrogenolysis catalyst, a preparation method and application thereof, and a method for preparing isopropylbenzene from alpha, alpha-dimethylbenzyl alcohol. The catalyst comprises: element Pd, element W and a carrier; wherein, the ultraviolet Raman spectrum of the catalyst has a first signal peak at a wave number 807cm ‑1, a wave number 714cm ‑1 and a wave number 273cm ‑1, a second signal peak at a wave number 960-990cm ‑1, and a third signal peak at a wave number 300-360cm ‑1 and a wave number 880-940cm ‑1. In the preparation method of the catalyst, the W doping is directly introduced into the preparation of the carrier, which is favorable for the anchoring of the carrier to tungsten species WOx, effectively improves the dispersibility of W, and supposedly, the tungsten species introduced by the direct doping is an amorphous phase low polymerization state WO X species, and the formation of the WO X species is favorable for improving the activity of the catalyst.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a hydrogenolysis catalyst, a preparation method and application thereof, and a method for preparing isopropylbenzene from alpha, alpha-dimethylbenzyl alcohol.
Background
Propylene oxide (PropyleneOxide, PO for short) is an important organic chemical raw material, and is mainly used for producing polyether polyol, propylene glycol ether and the like. Currently, commercial production methods of PO mainly include a chlorohydrin method, a co-oxidation method (PO/SM), a cumene peroxide cycle method (CHP), and a hydrogen peroxide direct oxidation method (HPPO). The CHP method for producing propylene oxide is not affected by the price fluctuation of the joint product, has no pollution to the environment and little investment, is an environment-friendly clean production process, is successfully developed by Japanese Sumitomo chemical company at the earliest time, and comprises the procedures of cumene oxidation, propylene epoxidation, alpha-dimethylbenzyl alcohol hydrogenolysis (DMBA) and the like.
In the prior art, the modification of the catalyst is mainly focused on improving the activity and selectivity of the hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol, while the stability of the hydrogenolysis catalyst is less involved.
The conversion rate of the cumene prepared by hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol can reach 100 percent and the selectivity of the cumene can reach 97.5 percent by taking Cu-Cr oxide as a catalyst in US664613B2, but the copper-based catalyst is easy to sinter in the reaction with larger heat release, the long-term stability of the catalyst is problematic, and the industrial application is not facilitated.
CN114042460A adopts niobium and tungsten to help improve the acidity of Ni-based catalyst, thereby improving the conversion rate of a non-noble metal catalytic system and improving the catalytic activity, but a high content of Ni agent easily causes hydrogenation of benzene ring to generate isopropyl cyclohexane, and reduces the selectivity of the catalyst.
By the method, the novel preparation method of the alpha, alpha-dimethylbenzyl alcohol by hydrogenolysis is provided for solving the problems of low selectivity of the catalyst cumene and the like in the existing cumene preparation technology, and the possibility is provided for realizing the hydrogenolysis of the alpha, alpha-dimethylbenzyl alcohol by one step.
In the prior art, a W/Al 2O3 catalytic system prepared by adopting an isovolumetric impregnation method exists, and the change of the roasting temperature is found to cause the formed WOx to be in different aggregation states, but the acid contribution to the catalyst is small, and the activity of the catalyst is improved to a limited extent.
Disclosure of Invention
The invention aims to solve the problems of low reactant conversion rate and low product selectivity of a hydrogenolysis catalyst in the prior art, and provides a hydrogenolysis catalyst, a preparation method and application thereof, and a method for preparing isopropylbenzene from alpha, alpha-dimethylbenzyl alcohol.
In order to achieve the above object, the present invention provides, in a first aspect, a hydrogenolysis catalyst comprising: element Pd, element W and a carrier; wherein, the ultraviolet Raman spectrum of the catalyst has a first signal peak at a wave number 807cm -1, a wave number 714cm -1 and a wave number 273cm -1, a second signal peak at a wave number 960-990cm -1, and a third signal peak at a wave number 300-360cm -1 and a wave number 880-940cm -1.
In a second aspect, the present invention provides a method for preparing the catalyst according to the present invention, which comprises:
a. mixing a carrier source, a precursor containing element W, an organic acid and a binder, molding, drying for the first time, and roasting for the first time to obtain a carrier;
b. and c, contacting the carrier prepared in the step a with a solution of a precursor containing the element Pd, filtering, washing, drying for the second time, and roasting for the second time to obtain the catalyst.
The third aspect of the present invention provides a use of the catalyst of the present invention in the hydrogenolysis of a feedstock comprising a structure as shown in formula (a),
Wherein R 1 is selected from aromatic groups; r 2 is selected from C1-C4 alkyl, preferably from methyl or ethyl; r 3 is selected from C1-C4 alkyl, preferably from methyl or ethyl.
In a fourth aspect, the present application provides a process for the preparation of cumene from α, α -dimethylbenzyl alcohol by contacting a feedstock comprising α, α -dimethylbenzyl alcohol and optionally a solvent with a hydrogen-containing stream in the presence of a catalyst according to the present application, preferably under conditions comprising:
The molar ratio of the hydrogen-containing stream to the raw material containing alpha, alpha-dimethylbenzyl alcohol, calculated as hydrogen, calculated as alpha, alpha-dimethylbenzyl alcohol, is not less than 4.5, preferably in the range of 5 to 10; and/or
The reaction temperature is 150-240 ℃, preferably 160-230 ℃; and/or
The reaction pressure is 0.5-5.0MPa, preferably 1.0-4.0MPa; and/or
The volume space velocity of the alpha, alpha-dimethylbenzyl alcohol is 1.0-10.0h -1, preferably 1-6h -1;
preferably, the solvent is selected from cumene.
Through the technical scheme, the invention has the following beneficial effects:
the catalyst with the characteristics of the invention has the advantages of high reactant conversion rate and high product selectivity.
In the preparation method of the catalyst, the W doping is directly introduced into the preparation of the carrier, which is favorable for the anchoring of the carrier to tungsten species WOx, effectively improves the dispersibility of W, and supposedly, the tungsten species introduced by the direct doping is an amorphous phase low polymerization state WO X species, and the formation of the WO X species is favorable for improving the activity of the catalyst.
The catalyst provided by the invention is applied to the DMBA hydrogenolysis reaction, and the synergistic effect between Pd and W is found, so that the activity and selectivity of the DMBA hydrogenolysis reaction can be effectively improved.
Drawings
FIG. 1 is a graph showing the ultraviolet Raman spectra of the catalysts prepared in example 1 and comparative examples 2-3 of the present invention;
FIG. 2 is XRD patterns of the catalysts prepared in example 1 and comparative examples 2-3 of the present invention;
FIG. 3 is a NH 3 -TPD plot of the catalysts of inventive example 1 and comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect the present invention provides a hydrogenolysis catalyst comprising: element Pd, element W and a carrier; wherein, the ultraviolet Raman spectrum of the catalyst has a first signal peak at a wave number 807cm -1, a wave number 714cm -1 and a wave number 273cm -1, a second signal peak at a wave number 960-990cm -1, and a third signal peak at a wave number 300-360cm -1 and a wave number 880-940cm -1.
The catalyst with the characteristics of the invention has the advantages of high activity (high conversion rate of reactants) and high product selectivity.
According to a preferred embodiment of the invention, the intensity of the first signal peak in the ultraviolet raman spectrum of the catalyst is 0-50.0% of the total intensity of the first signal peak and the second signal peak, and is not 0. By adopting the foregoing preferences, the activity of the catalyst, as well as the reactant selectivity, can be further improved.
According to a preferred embodiment of the invention, the XRD pattern of the catalyst is such that no signal peaks are present at 23.2 °, 23.6 °, 24.2 ° 2θ.
According to a preferred embodiment of the present invention, the support is selected from at least one of an alumina support, a silica support and a zirconia support.
According to a preferred embodiment of the invention, the catalyst comprises: 0.1-2.0wt% of elemental Pd;0.5-15wt% of element W;84.9-97.5wt% carrier.
In a second aspect, the present invention provides a method for preparing the catalyst according to the present invention, which comprises:
a. mixing a carrier source, a precursor containing element W, an organic acid and a binder, molding, drying for the first time, and roasting for the first time to obtain a carrier;
b. and c, contacting the carrier prepared in the step a with a solution of a precursor containing the element Pd, filtering, washing, drying for the second time, and roasting for the second time to obtain the catalyst.
In the preparation method of the catalyst, the W doping is directly introduced into the preparation of the carrier, which is favorable for the anchoring of the carrier to tungsten species WOx, effectively improves the dispersibility of W, and supposedly, the tungsten species introduced by the direct doping is an amorphous phase low polymerization state WO X species, and the formation of the WO X species is favorable for improving the activity of the catalyst.
In the present invention, the molding means may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the molding means includes kneading, extruding.
In the present invention, the optional range of the precursor containing element W is wide, and according to a preferred embodiment of the present invention, the precursor containing element W is a compound containing element W, preferably a tungstate, and more preferably at least one selected from ammonium tungstate, ammonium paratungstate, and ammonium metatungstate.
In the present invention, the optional range of the precursor containing element Pd is wide, and according to a preferred embodiment of the present invention, the precursor containing element Pd is a compound containing element Pd, preferably the compound containing Pd is at least one selected from palladium chloride, palladium nitrate, ammonium chloropalladate, palladium acetate and palladium sulfate.
According to a preferred embodiment of the present invention, the support source is selected from at least one of an alumina support source, a silica support source and a zirconia support source.
According to a preferred embodiment of the invention, the organic acid is a C1-C6 organic acid, preferably at least one selected from the group consisting of citric acid, acetic acid, formic acid. By adopting the foregoing preferences, the reactivity of the reaction and the product selectivity can be further improved.
In the present invention, the optional range of the binder is wide, and according to a preferred embodiment of the present invention, the binder is selected from one or both of nitric acid and sesbania powder.
In the present invention, the conditions for the first drying may be conventional choices in the art, and according to a preferred embodiment of the present invention, the conditions for the first drying include: the temperature is 60-120deg.C, the time is 2-24h, preferably 80-100deg.C, and the time is 4-12h. The embodiment of the invention takes 90 ℃ temperature and 8h time as examples to illustrate the advantages of the invention.
In the present invention, the conditions of the first firing may be conventional choices in the art, and according to a preferred embodiment of the present invention, the conditions of the first firing include: the temperature is 500-1200deg.C, the time is 2-12h, preferably 600-1000deg.C, and the time is 3-6h. The embodiment of the invention takes 800 ℃ temperature and 8h time as examples to illustrate the advantages of the invention.
In the present invention, the conditions for the second drying may be conventional choices in the art, and according to a preferred embodiment of the present invention, the conditions for the second drying include: the temperature is 60-120deg.C, the time is 2-24h, preferably 80-100deg.C, and the time is 4-12h. The embodiment of the invention takes 90 ℃ temperature and 8h time as examples to illustrate the advantages of the invention.
In the present invention, the conditions for the second firing may be conventional choices in the art, and according to a preferred embodiment of the present invention, the conditions for the second firing include: the temperature is 300-800 ℃, the time is 2-12h, the preferable temperature is 400-600 ℃, and the time is 4-12h. The embodiment of the invention takes the temperature of 500 ℃ and the time of 4 hours as examples to illustrate the advantages of the invention.
In the present invention, the conditions of the contacting may be conventional choices in the art, and according to a preferred embodiment of the present invention, the conditions of the contacting include: the temperature is 30-100deg.C, the time is 10-60min, preferably 30-90deg.C, and the time is 20-50min. The embodiment of the invention takes the excessive dipping method for contact, the temperature is 50 ℃ and the time is 20min as an example to illustrate the advantages of the invention.
The third aspect of the present invention provides a use of the catalyst of the present invention in the hydrogenolysis of a feedstock comprising a structure as shown in formula (a),
Wherein R 1 is selected from aromatic groups; r 2 is selected from C1-C4 alkyl, preferably from methyl or ethyl; r 3 is selected from C1-C4 alkyl, preferably from methyl or ethyl.
The catalyst of the invention is applied to the hydrogenolysis reaction of the raw materials, and has excellent activity and product selectivity of the hydrogenolysis reaction.
In a fourth aspect, the present invention provides a process for the preparation of cumene from α, α -dimethylbenzyl alcohol by contacting a feedstock comprising α, α -dimethylbenzyl alcohol and optionally a solvent with a hydrogen-containing stream in the presence of a catalyst according to the present invention.
In the present invention, the conditions of the contact reaction may be a conventional choice in the art.
According to a preferred embodiment of the present invention, the conditions of the contact reaction include: the molar ratio of the hydrogen-containing stream to the feed containing alpha, alpha-dimethylbenzyl alcohol, calculated as hydrogen, is not less than 4.5, preferably in the range of 5 to 10, calculated as alpha, alpha-dimethylbenzyl alcohol.
According to a preferred embodiment of the present invention, the conditions of the contact reaction include: the reaction temperature is 150 to 250 ℃, preferably 160 to 230 ℃.
According to a preferred embodiment of the present invention, the conditions of the contact reaction include: the reaction pressure is 0.1 to 5.0MPa, preferably 1.0 to 4.0MPa.
According to a preferred embodiment of the present invention, the conditions of the contact reaction include: the volume space velocity of the alpha, alpha-dimethylbenzyl alcohol is 1.0-10.0h -1, preferably 1-6h -1.
By adopting the aforementioned preferable contact conditions, the activity of the reaction and the product selectivity can be further improved.
In the present invention, the solvent may be selected by a conventional technique in the art, and according to a preferred embodiment of the present invention, the solvent is selected from cumene.
According to a preferred embodiment of the present invention, the content of α, α -dimethylbenzyl alcohol in the α, α -dimethylbenzyl alcohol-containing feedstock is in the range of from 10 to 100% by weight, preferably in the range of from 50 to 70% by weight.
According to a preferred embodiment of the present invention, the raw material containing α, α -dimethylbenzyl alcohol further contains 0.01 to 3.00% by weight of α -methylstyrene.
In the present invention, the source of the raw material containing α, α -dimethylbenzyl alcohol is not particularly limited, and according to a preferred embodiment of the present invention, the raw material containing α, α -dimethylbenzyl alcohol is at least one selected from the group consisting of products of a cumene peroxide recycle process and a dicumyl peroxide technology.
The present invention will be described in detail by examples. In the following examples, unless otherwise specified, the raw materials were all commercially available.
The content of each component is analyzed by 7890 gas chromatograph of AgilentTechnologies company in the United states and measured by area normalization method;
The Raman spectrum is obtained by testing by HoribaJYLabRAMARAMIS laser Raman spectrometer, the wavelength of the laser used for testing is 532nm, grating 1200-grmm -1, and the spectrum range is 100-1200cm -1.
The crystal structure and phase composition of the catalyst were determined by powder X-ray diffraction (XRD) testing. The test was performed on BrukerD a 8 advanced X-ray diffractometer using cukα1 source (λ= 0.15405 nm) and graphite monochromator with a tube pressure of 40kV, a tube flow of 50mA and a scanning range of 5-90 °.
Acid profile: ammonia adsorption-temperature programmed desorption (NH 3 -TPD) testing was performed on a chemisorber (ALTAMIRAAMI-3300), 0.15g of sample was weighed, purged with N 2 at 600℃for 60min, cooled to 25℃and saturated with 10% NH 3/N2 gas mixture for 30min to NH 3 adsorption, and the physisorbed NH 3 was removed in the He atmosphere. Subsequently, the temperature was programmed to 600℃at 10℃min -1, and the change in concentration of NH 3 in the exhaust was detected using a TCD detector.
The method for calculating the conversion rate of the alpha, alpha-dimethylbenzyl alcohol comprises the following steps:
conversion = (molar amount of α, α -dimethylbenzyl alcohol in starting material-molar amount of α, α -dimethylbenzyl alcohol in product)/molar amount of α, α -dimethylbenzyl alcohol in starting material;
The selectivity calculation method of the isopropylbenzene comprises the following steps:
selectivity = (molar amount of cumene product-molar amount of cumene in starting material)/(molar amount of α, α -dimethylbenzyl alcohol in starting material-molar amount of α, α -dimethylbenzyl alcohol in product).
Example 1
Adding ammonium metatungstate aqueous solution, citric acid and sesbania powder into Al 2O3 raw powder, kneading, extruding, drying at 90 ℃ for 8 hours, and roasting at 800 ℃ for 4 hours to obtain an alumina carrier containing W (W-Al 2O3). The method comprises the steps of taking W-Al 2O3 as a carrier and palladium chloride as a precursor, putting the carrier into a palladium chloride aqueous solution, stirring and heating to 50 ℃, immersing for 20min, filtering, washing with deionized water, drying at 90 ℃ for 8h, roasting at 500 ℃ for 4h, and preparing Pd/W-Al 2O3 by adopting an excessive immersion method, wherein the Pd content is 0.5wt%, the W content is 7wt% and the alumina carrier content is 92.5wt%. Detecting an ultraviolet Raman spectrum of the catalyst, as shown in FIG. 1, wherein the ultraviolet Raman spectrum of the catalyst has a first signal peak at a wave number of 807cm -1, a wave number of 714cm -1, a wave number of 273cm -1, a second signal peak at a wave number of 960-990cm -1, a third signal peak at a wave number of 300-360cm -1,880-940cm-1, and the intensity of the first signal peak is 46% of the total intensity of the first signal peak and the second signal peak; XRD spectrum, as in fig. 2, shows no signal peaks at 23.2 °, 23.6 °, 24.2 ° 2θ; the acidity curve is shown in FIG. 3.
Example 2
The preparation method was the same as in example 1, except that Pd content in Pd/W-SiO 2 prepared by using silica sol as a carrier source and organic acid as acetic acid was 0.5wt%, W content was 10wt% and silica carrier content was 89.5wt%. The ultraviolet raman spectrum of the catalyst was detected, and the intensity of the first signal peak was 49% of the total intensity of the first signal peak and the second signal peak.
Example 3
The preparation method was the same as in example 1 except that Pd was 0.5wt% in the Pd/W-Al 2O3 prepared, W was 4wt% and alumina carrier was 95.5wt%. The ultraviolet raman spectrum of the catalyst was detected, and the intensity of the first signal peak was 34% of the total intensity of the first signal peak and the second signal peak.
Example 4
The preparation method was the same as in example 1 except that Pd was 0.5wt% in the Pd/W-Al 2O3 prepared, W was 20wt% and alumina carrier was 79.5wt%. The ultraviolet Raman spectrum of the catalyst is detected, and the intensity of the first signal peak is 55.0% of the total intensity of the first signal peak and the second signal peak.
Example 5
The procedure of example 1 was repeated except that no organic acid was added to prepare a carrier having a Pd/W-Al 2O3 content of 0.5wt%, a W content of 7wt% W and an alumina carrier content of 92.5wt%. The ultraviolet raman spectrum of the catalyst was detected, and the intensity of the first signal peak was 51.3% of the total intensity of the first signal peak and the second signal peak.
Comparative example 1
The preparation method is the same as in example 1, except that ammonium meta-tungstate is not added in the preparation of the alumina carrier, the Pd content in the obtained Pd/Al 2O3 catalyst is 0.5wt%, the alumina carrier content is 99.5wt%, and the ultraviolet Raman spectrum diagram of the catalyst is detected, wherein no first signal peak, no second signal peak and no third signal peak are found. The acidity curve is shown in FIG. 3.
Comparative example 2
The preparation method was the same as in example 1 except that ammonium meta-tungstate was not added in the preparation of the alumina carrier. The prepared alumina carrier is immersed in an ammonium metatungstate aqueous solution by an isovolumetric method, dried at 90 ℃ for 8 hours and roasted at 800 ℃ for 4 hours, and the W modified alumina carrier (W/Al 2O3 is recorded). The ultraviolet raman spectrum of the catalyst was examined using W/Al 2O3 as a carrier and Pd supported in the same manner to prepare W/Pd/Al 2O3 in which the Pd content was 0.5wt%, the W content was 7wt% W, the alumina carrier content was 92.5wt%, as shown in fig. 1, the first signal peak was not seen, the third signal peak was not seen, and the XRD spectrum, as shown in fig. 2, showed signal peaks at 23.2 °, 23.6 °, and 24.2 ° in 2θ, as compared with example 1.
Comparative example 3
The difference from comparative example 2 is that the prepared alumina carrier phase was supported with Pd and then with W to obtain a Pd/W/Al 2O3 -based catalyst, wherein the Pd content was 0.5wt%, the W content was 7wt% W, the alumina carrier content was 92.5wt%, and the ultraviolet Raman spectrum of the catalyst was examined, as shown in FIG. 1, the intensity of the first signal peak was 61.3% of the total intensity of the first signal peak and the second signal peak, no third signal peak was seen, and the XRD spectrum was examined, as shown in FIG. 2, and signal peaks were present at 2.2 °, 23.6 °, 24.2℃as compared with example 1.
Example 6
The catalysts prepared in examples and comparative examples 1-5 and comparative examples 1-3 were used in the preparation of cumene by hydrogenolysis of α, α -dimethylbenzyl alcohol:
Catalyst evaluation method: the prepared catalyst is filled into a fixed bed reactor for hydrogenolysis reaction, the catalyst is reduced at 160 ℃ for 8 hours, 51.00 weight percent of isopropylbenzene, 46.00 weight percent of alpha, alpha-dimethylbenzyl alcohol, 0.075 weight percent of alpha-methylstyrene and impurities in benzyl alcohol raw materials, the reaction pressure is 2.0MPa, the inlet temperature is 160 ℃, the molar ratio of H 2 to benzyl alcohol is 6.0, and the liquid volume space velocity is 2 hours -1. Liquid phase products were analyzed using a 7890 gas chromatograph from AgilentTechnologies, U.S. and quantified using an area normalization method, and conversion and selectivity were calculated.
Catalyst performance:
As can be seen from the results in Table 1 and FIG. 3, the catalyst prepared by the method of the present invention has stronger acidity, is used for hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol, has higher catalytic activity and selectivity, and is suitable for industrial application.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A hydrogenolysis catalyst characterized in that the catalyst comprises: element Pd, element W and a carrier; wherein, the ultraviolet Raman spectrum of the catalyst has a first signal peak at a wave number 807cm -1, a wave number 714cm -1 and a wave number 273cm -1, a second signal peak at a wave number 960-990cm -1, and a third signal peak at a wave number 300-360cm -1 and a wave number 880-940cm -1.
2. The catalyst of claim 1, wherein the intensity of the first signal peak in the ultraviolet raman spectrum of the catalyst is 0-50.0% of the total intensity of the first signal peak and the second signal peak, and is not 0; and/or
The XRD pattern of the catalyst has no signal peaks at 23.2 degrees, 23.6 degrees and 24.2 degrees of 2 theta.
3. The catalyst according to claim 1 or 2, wherein the support is selected from at least one of an alumina support, a silica support and a zirconia support.
4. A catalyst according to any one of claims 1 to 3, wherein the catalyst comprises: 0.1-2.0wt% of elemental Pd;0.5-15wt% of element W;84.9-97.5wt% carrier.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, which comprises:
a. Mixing a carrier source, a precursor containing element W and a binder, forming, first drying and first roasting to obtain a carrier, and preferably adding an organic acid during the mixing;
b. and c, contacting the carrier prepared in the step a with a solution of a precursor containing the element Pd, filtering, washing, drying for the second time, and roasting for the second time to obtain the catalyst.
6. The preparation method according to claim 5, wherein,
The precursor containing the element W is a compound containing the element W, preferably tungstate, and more preferably at least one selected from ammonium tungstate, ammonium paratungstate and ammonium metatungstate; and/or
The precursor containing the element Pd is a compound containing the element Pd, and preferably the compound containing the element Pd is at least one selected from palladium chloride, palladium nitrate, ammonium chloropalladate, palladium acetate and palladium sulfate; and/or
The carrier source is selected from at least one of an alumina carrier source, a silica carrier source and a zirconia carrier source; and/or
The organic acid is C1-C6 organic acid, preferably at least one selected from citric acid, acetic acid and formic acid; and/or
The binder is one or two selected from nitric acid and sesbania powder.
7. The preparation method according to claim 5 or 6, wherein,
The first drying conditions include: the temperature is 60-120 ℃, the time is 2-24h, the preferable temperature is 80-100 ℃, and the time is 4-12h; and/or
The conditions of the first firing include: the temperature is 500-1200 ℃, the time is 2-12h, the preferable temperature is 600-1000 ℃ and the time is 3-6h; and/or
The second drying conditions include: the temperature is 60-120 ℃, the time is 2-24h, the preferable temperature is 80-100 ℃, and the time is 4-12; and/or
The conditions of the second firing include: the temperature is 300-800 ℃, the time is 2-12h, the preferable temperature is 400-600 ℃, and the time is 4-12h; and/or
The conditions of the contacting include: the temperature is 30-100deg.C, the time is 10-60min, preferably 30-90deg.C, and the time is 20-50min.
8. The use of the catalyst according to any one of claim 1 to 4 for the hydrogenolysis of a feedstock comprising a structure represented by formula (a),
Wherein R 1 is selected from aromatic groups; r 2 is selected from C1-C4 alkyl, preferably from methyl or ethyl; r 3 is selected from C1-C4 alkyl, preferably from methyl or ethyl.
9. A process for the preparation of cumene from alpha, alpha-dimethylbenzyl alcohol, characterized in that a feed comprising alpha, alpha-dimethylbenzyl alcohol and optionally a solvent is contacted with a hydrogen-containing stream in the presence of a catalyst according to any one of claims 1 to 4,
Preferably, the conditions of the contact reaction include:
The molar ratio of the hydrogen-containing stream to the raw material containing alpha, alpha-dimethylbenzyl alcohol, calculated as hydrogen, calculated as alpha, alpha-dimethylbenzyl alcohol, is not less than 4.5, preferably in the range of 5 to 10; and/or
The reaction temperature is 150-250 ℃, preferably 160-230 ℃; and/or
The reaction pressure is 0.1-5.0MPa, preferably 1.0-4.0MPa; and/or
The volume space velocity of the alpha, alpha-dimethylbenzyl alcohol is 1.0-10.0h -1, preferably 1-6h -1;
preferably, the solvent is selected from cumene.
10. The process according to claim 9, wherein the α, α -dimethylbenzyl alcohol content of the α, α -dimethylbenzyl alcohol-containing feedstock is from 10 to 100wt%, preferably from 10 to 70wt%;
Preferably, the raw material containing the alpha, alpha-dimethylbenzyl alcohol also contains 0.01-1.00wt% of alpha-methylstyrene, more preferably, the raw material containing the alpha, alpha-dimethylbenzyl alcohol is selected from one or two of products of a dicumyl peroxide recycling method and dicumyl peroxide technology.
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