CN115487821A - Application of inorganic oxide supported multi-metal catalyst in catalyzing hydroquinone or bisphenol A hydrogenation reaction - Google Patents
Application of inorganic oxide supported multi-metal catalyst in catalyzing hydroquinone or bisphenol A hydrogenation reaction Download PDFInfo
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Abstract
The invention discloses an application of an inorganic oxide supported multi-metal catalyst in catalyzing hydroquinone or bisphenol A hydrogenation reaction, belonging to the technical field of hydrogenation of heterogeneous catalysts. The catalyst mainly comprises two parts, namely an active component and a carrier, wherein the carrier is an inorganic oxide carrier; the active component is a multi-metal species, comprising 2-3 metal species, namely a first metal, a second metal and a third metal respectively, the active component is highly dispersed on a carrier by means of impregnation and the like, and hydroquinone or bisphenol A can be converted into 1,4-cyclohexanediol or hydrogenated bisphenol A with high activity, high selectivity and high stability in a fixed bed reactor under the action of mild temperature and pressure and the catalyst, so that the production efficiency is greatly improved, and the catalyst is more suitable for industrial application processes.
Description
Technical Field
The invention belongs to the technical field of hydrogenation of heterogeneous catalysts, and particularly relates to an application of an inorganic oxide-loaded multi-metal catalyst in catalyzing hydroquinone or bisphenol A hydrogenation reaction under mild conditions.
Background
1,4-cyclohexanediol is an important fine chemical and an intermediate, and is widely applied to the fields of pesticides, organic synthesis, new materials of liquid crystals and the like. At present, the method is mainly used for synthesizing inositol phospho-kinase inhibitors, benzotriazol medicaments, succinyl sulphathiazole, HMGCoA reductase, tetracyanoquinodimethane and the like. The 1,4-cyclohexanediol with pure spectrum as a new material monomer can be used for synthesizing liquid crystal materials, biological controller markers, organic electric materials and the like. At present, with the improvement of national economic level and the continuous progress of science and technology, the application field of 1,4-cyclohexanediol is wider and wider.
5363A synthetic method of 1,4-cyclohexanediol generally adopts a catalytic benzene ring hydrogenation mode by taking hydroquinone as a raw material. At present, catalysts for preparing 1,4-cyclohexanediol by hydroquinone hydrogenation mainly comprise three types, namely Raney Ni and Ru supported catalysts and Ni supported catalysts. The Ru-based catalyst has higher hydroquinone hydrogenation activity, but because Ru species easily break C-O bonds, the key problem of poor selectivity of 1,4-cyclohexanediol generally exists, for example, the selectivity of 1,4-cyclohexanediol obtained by hydrogenating Ru/C hydroquinone in 201019100011.6 is only about 80%. The Raney Ni catalyst has relatively poor activity in the hydrogenation process, the hydrogenation process (generally more than 150 ℃) needs to be carried out at a higher temperature, a large amount of alkali species needs to be added to improve the selectivity of 1,4-cyclohexanediol to about 93%, and the problem of environmental pollution is aggravated by the addition of the alkali species. Patent 200710061447.X indicates that Raney Ni catalyst can catalyze hydroquinone to prepare 1,4-cyclohexanediol by taking water and alkali solution as solvents under the conditions of certain temperature and pressure. The Ru-based catalyst and Raney Ni catalyst reported at present generally adopt a batch reactor, and have the problems of poor operation continuity, complicated separation operation and the like although the activity is high. In contrast, the fixed bed reactor can simplify the separation process, improve the productivity and is more suitable for industrial production, but the activity is generally obviously lower than that of a full back-mixing tank type reaction system because the fixed bed is generally a plug flow reaction model.
Thus, the hydroquinone preparation reported at present is hydrogenated1,4 cyclohexanediol has the following disadvantages: 1) Most of the kettle type hydrogenation processes have the problems of poor operation continuity, low productivity, complicated separation operation and the like; 2) Under the condition of no addition of an auxiliary agent or KOH, the selectivity of 1,4-cyclohexanediol is generally lower than 90 percent, and the auxiliary agents such as KOH and the like bring inevitable environmental pollution problems while improving the performance of the catalyst; 3) Alkali-adjuvant-modified Ni/gamma-Al reported at present 2 O 3 Requires a reaction at a higher temperature (>150 ℃) and has lower hydrogenation activity.
In addition, hydrogenated bisphenol a is an important basic chemical raw material and medical intermediate, mainly used as a raw material for polycarbonate, polyacrylic resin, unsaturated resin, epoxy resin, and the like, and a resin synthesized from hydrogenated bisphenol a has more excellent performance than a resin synthesized from bisphenol a, and hydrogenation of bisphenol a is an important route for synthesizing hydrogenated bisphenol a.
Therefore, the development of a high-selectivity, high-activity and high-stability fixed bed reaction system capable of realizing continuous production under mild conditions becomes a key means for promoting the industrialization of the preparation of 1,4-cyclohexanediol by hydroquinone hydrogenation or the preparation of bisphenol A by bisphenol A hydrogenation.
Disclosure of Invention
The technical problems stated in the background art are solved. The invention aims to provide an application of an inorganic oxide supported multi-metal catalyst in catalyzing hydroquinone or bisphenol A hydrogenation reaction under mild conditions, wherein the multi-metal catalyst takes a first metal Re species and a second metal Co, ni, fe and the like as main hydrogenation active centers, improves the hydrogenation activity and selectivity through the interaction of metal species, effectively reduces the reaction temperature to a great extent, and realizes the hydrogenation process under the low-temperature condition; la, ce and the like are used as third metals and used as stability additives, so that the stability of the hydrogenation process is improved, the first metal and the second metal are not easy to aggregate and inactivate, silylation modification is completed by introducing silicon species, the hydrogenation stability is further improved, inactivation is inhibited, and the method has important significance for improving the selectivity and the production efficiency of 1,4-cyclohexanediol and hydrogenated bisphenol A and reducing the cost, and has important significance for realizing industrial application.
The technical scheme of the invention is as follows:
the application of an inorganic oxide carrier-supported multi-metal catalyst in the reaction of preparing 1,4-cyclohexanediol or bisphenol A from hydroquinone through hydrogenation to prepare bisphenol A is characterized in that the multi-metal catalyst consists of a main active component and a carrier, wherein the main active component is a first metal and a second metal or the first metal, the second metal and a third metal, and the first metal is Re; the second metal is one or more than two of Co, ni, fe and Cu; the third metal is one or more of La, ce and Y, and the carrier is an inorganic oxide carrier.
Based on the technical scheme, the multi-metal catalyst is further modified by alkylation with silicon.
Based on the technical scheme, the content of the first metal is 0.01-10.0 wt% of the weight of the catalyst, and preferably 0.1-2.0 wt% of the total mass of the catalyst; the content of the second metal is 0.01-30.0 wt% of the weight of the catalyst, preferably 0.1-15.0 wt% of the total mass of the catalyst; the third metal content is 0.01-30.0 wt% of the catalyst weight, preferably 0.1-15.0 wt% of the total catalyst mass.
Based on the technical scheme, further, the inorganic oxide has a porous structure, and the pore volume range of the inorganic oxide is 0.1-10.0 cm 3 G, the pore diameter distribution is 0.2-70.0 nm, the specific surface area range is 20-500 m 2 /g。
Based on the technical scheme, the carrier is gamma-Al 2 O 3 、TiO 2 Or a combination of one or two or more kinds of ZnO.
Based on the technical scheme, further, the preparation method of the inorganic oxide carrier-supported multi-metal catalyst mainly comprises the following steps:
dissolving precursors of a first metal and a second metal, or dissolving the precursors of the first metal, the second metal and a third metal in water, soaking the obtained solution on an inorganic oxide carrier in an equal volume or in an excessive amount, evaporating the solvent in a water bath at 30-80 ℃, drying for 5-15 h at 100-150 ℃ in an oven, and roasting for 1-10 h at 300-800 ℃ in a muffle furnace to obtain the catalyst;
or dissolving precursors of the first metal and the second metal, or dissolving the precursors of the first metal, the second metal and the third metal in water, soaking the obtained solution on an inorganic oxide carrier in an equal volume or excessively, evaporating the solvent in a water bath at 30-80 ℃, drying the solvent in an oven at 100-150 ℃ for 5-15 h, adding the obtained catalyst into a silane species solution, maintaining the pH value at 4-9, stirring for 1-8 h, washing and filtering, drying the catalyst in the oven at 100-150 ℃ for 5-15 h, and roasting in a muffle furnace at 300-800 ℃ for 1-10 h to obtain the catalyst.
Based on the technical scheme, the silane species in the silane species solution is one or more than two of methyl triethoxysilane, tetraethyl orthosilicate, 3-propylamine triethoxysilane and gamma-mercaptopropyl triethoxysilane; the solvent is a mixed solution of an organic solvent and water, the organic solvent comprises methanol, ethanol, propanol, tetrahydrofuran and dimethyl sulfoxide, and the concentration of silane species is 0.001-1.0mol/L.
Based on the technical scheme, the roasting temperature is 400-600 ℃, and the roasting time is 2-8.
Based on the technical scheme, further, the Re metal precursor is KReO 4 、Re 2 O 7 、NH 4 ReO 4 、HReO 4 、NaReO 4 One or more than two of the above; the second metal precursor is Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 O、NiSO 4 ·7H 2 O、CoSO 4 ·7H 2 O、Fe(NO 3 ) 3 ·9H 2 O、FeCl 3 ·6H 2 O、Fe 2 (SO 4 ) 3 One or more than two of them; the third metal species is La (NO) 3 ) 3 ·6H 2 O、LaCl 3 ·6H 2 O、La 2 (SO 4 ) 3 ·9H 2 O、Ce(NO 3 ) 3 ·6H 2 O、CeCl 3 、Ce 2 (SO 4 ) 3 ·8H 2 O、Y(NO 3 ) 3 ·6H 2 One or two or more of O.
Based on the technical scheme, a main reactor adopted in the hydrogenation reaction process is a fixed bed reactor, and the material of the reactor is 316L; the reaction temperature is 50-200 ℃, and the reaction pressure is 0.1-4.0 MPa.
Based on the technical scheme, the multi-metal catalyst is subjected to in-situ pre-reduction activation in the reactor.
Based on the technical scheme, further, the temperature in the pre-reduction activation process is 200-700 ℃, the pressure is 0.1-2.0 MPa, and the gas volume space velocity is 2000-8000h -1 。
Based on the technical scheme, the specific process of the hydrogenation reaction is to add H 2 And pumping the hydroquinone or bisphenol A solution into a fixed bed reactor filled with the multi-metal catalyst for selective hydrogenation, wherein the target product is 1,4-cyclohexanediol or hydrogenated bisphenol A.
Based on the technical scheme, further, the temperature of the selective hydrogenation reaction is 50-100 ℃, the pressure is 0.1-3.0 MPa, and the liquid volume space velocity is 0.1-500 h -1 ，H 2 And hydroquinone or H 2 And bisphenol A in a molar ratio of 4000 to 3: the solvent of the hydroquinone solution or the bisphenol A solution is one or the combination of more than two of water, isopropanol, ethanol, methanol and acetone.
The invention has the beneficial effects that:
1. according to the inorganic oxide supported multi-metal catalyst, the first metal and the second metal are hydrogenation active sites, the hydrogenation capacity is greatly improved through strong interaction, the hydrogenation reaction temperature is effectively and greatly reduced, the third metal or the silane modified component can effectively improve the hydrogenation stability of the catalyst, the excellent catalytic effect (high selectivity, high activity, high stability and mild conditions) of 1,4-cyclohexanediol prepared by hydroquinone hydrogenation or bisphenol A prepared by bisphenol A hydrogenation is obtained, the production efficiency is greatly improved, and the inorganic oxide supported multi-metal catalyst is more suitable for industrial application processes.
2. Compared with the existing kettle type hydrogenation technology of Raney Ni and Ru-based catalysts for hydrogenation of supported hydroquinone, the inorganic oxide supported multi-metal catalyst hydrogenation technology has the advantages of high 1,4-cyclohexanediol selectivity, high hydrogenation activity, high stability, reaction under mild conditions, no addition of alkali species, environmental friendliness, high efficiency, applicability to a continuous fixed bed system and great reduction in cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention, reference will now be made briefly to the accompanying drawings, to which embodiments relate.
FIG. 1 is a graph showing the stability of the catalysts of the examples and comparative examples in the preparation of 1,4-cyclohexanediol by selective hydrogenation of hydroquinone.
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive exercise and falling into the scope of the present invention.
Example 1
Weighing 0.0625g KReO 4 、2.97g Co(NO 3 ) 2 ·6H 2 O、0.94g La(NO 3 ) 3 ·6H 2 O was dissolved in 10g of water and then impregnated with 6g of TiO 2 Evaporating the solvent in water bath at 40 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the supported Re-based catalyst-1.
Example 2
0.0522g Re is weighed 2 O 7 、2.43g CoCl 2 ·6H 2 O、0.79g La 2 (SO 4 ) 3 ·9H 2 O、0.93g Ce(NO 3 ) 3 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the Re-based catalyst-2.
Example 3
0.0579g of NH are weighed 4 ReO 4 、2.97g Ni(NO 3 ) 2 ·6H 2 O dissolved in 10g of waterThen impregnated with 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the supported Re-based catalyst-3.
Example 4
Weighing 0.0542g HReO 4 、2.43g NiCl 2 ·6H 2 O、0.78g La 2 (SO 4 ) 3 ·9H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 . Evaporating the solvent in water bath at 40 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 700 ℃ for 4h to obtain the Re-based catalyst-4.
Example 5
Weighing 0.0590g NaReO 4 、1.43g CoSO 4 ·7H 2 O、1.43g NiSO 4 ·7H 2 O、0.26g CeCl 3 、0.38g Ce 2 (SO 4 ) 3 ·8H 2 Dissolving O in 10g of water, then soaking 6g of ZnO, evaporating the solvent in a water bath at 40 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 700 ℃ for 4h to obtain the supported Re-based catalyst-5.
Example 6
0.0579g of NH are weighed 4 ReO 4 、1.38g Fe(NO 3 ) 3 ·9H 2 O、0.92g FeCl 3 ·6H 2 O、0.68g Fe 2 (SO 4 ) 3 、1.29g Y(NO 3 ) 3 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the supported Re-based catalyst-6.
Example 7
0.0290g NH was weighed out 4 ReO 4 、0.0261g Re 2 O 7 、2.86g NiSO 4 ·7H 2 O、0.52g CeCl 3 Dissolved in 10g of water and then impregnated with 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the supported Re-based catalyst-7.
Example 8
0.0579g of NH are weighed 4 ReO 4 、2.97g Ni(NO 3 ) 2 ·6H 2 O、0.94g La(NO 3 ) 3 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 Evaporating the solvent in water bath at 40 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the Re-based supported catalyst-8.
Example 9
0.0579g of NH are weighed 4 ReO 4 、2.97g Ni(NO 3 ) 2 ·6H 2 O、0.94g La(NO 3 ) 3 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 . Evaporating the solvent in water bath at 40 ℃, and drying in a 120 ℃ oven for 10h;15mL of tetraethyl orthosilicate, 40g of ethanol, 7.25mL of deionized water were mixed and the pH was maintained at 7-8 by NaOH and hydrochloric acid adjustment. Adding the dried catalyst, maintaining the pH value at 7-8, stirring for 3h, washing with deionized water, filtering, drying in an oven at 120 ℃ for 10h, and calcining at 500 ℃ for 4h to obtain the supported Re-based catalyst-9.
Example 10
0.0579g of NH are weighed 4 ReO 4 、2.97g Ni(NO 3 ) 2 ·6H 2 O、0.94g La(NO 3 ) 3 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 . Evaporating the solvent in water bath at 40 ℃, and drying in a 120 ℃ oven for 10h;15mL of methyltriethoxysilane, 40g of ethanol, 7.25mL of deionized water were mixed and the pH was maintained at 7-8 by NaOH and hydrochloric acid adjustment. Adding the dried catalyst, maintaining the pH value at 7-8, stirring for 3h, washing with deionized water, filtering, drying in an oven at 120 ℃ for 10h, and calcining at 500 ℃ for 4h to obtain the supported Re-based catalyst-10.
Example 11
0.0579g of NH are weighed 4 ReO 4 、2.97g Ni(NO 3 ) 2 ·6H 2 O、0.94g La(NO 3 ) 3 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 . Evaporating the solvent in water bath at 40 ℃, and drying in a 120 ℃ oven for 10h;15mL of 3-propylaminotriethoxysilane, 40g of ethanol, and 7.25mL of deionized water were mixed, and the pH was adjusted by NaOH and hydrochloric acid to be 7 to 8. Adding dried catalyst, maintaining pH at 7-8, stirring for 3 hr, washing with deionized water, filtering, oven drying at 120 deg.C for 10h, and calcining at 500 deg.C for 4 hr to obtain load Re-base catalyst-11.
Example 12
0.0522g Re is weighed 2 O 7 、2.86g CoSO 4 ·7H 2 O、0.52g CeCl 3 Dissolved in 10g of water and then impregnated with 6g of gamma-Al 2 O 3 (ii) a Evaporating the solvent in water bath at 50 ℃, and drying in an oven at 100 ℃ for 10h.15mL of gamma-mercaptopropyltriethoxysilane, 40g of ethanol, 7.25mL of deionized water were mixed and pH was maintained at 7-8 by NaOH and hydrochloric acid. Adding the dried catalyst, maintaining the pH value at 7-8, stirring for 3h, washing with deionized water, filtering, drying in an oven at 120 ℃ for 10h, and calcining at 500 ℃ for 4h to obtain the supported Re-based catalyst-12.
Comparative example 1
0.0579g of NH are weighed 4 ReO 4 Dissolved in 10g of water and then impregnated with 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the supported Re-based catalyst-13.
Comparative example 2
2.97g of Ni (NO) are weighed 3 ) 2 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the loaded Ni-based catalyst-14.
Comparative example 3
2.97g Co (NO) are weighed out 3 ) 2 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the supported Co-based catalyst-15.
Comparative example 4
2.97g Co (NO) are weighed out 3 ) 2 ·6H 2 O、0.93g Ce(NO 3 ) 3 ·6H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the loaded Co-Ce-based catalyst-16.
Comparative example 5
2.97g of Ni (NO) are weighed 3 ) 2 ·6H 2 O、0.78g La 2 (SO 4 ) 3 ·9H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the Ni-La-based catalyst-17.
Comparative example 6
0.0579g of NH are weighed 4 ReO 4 、0.78g La 2 (SO 4 ) 3 ·9H 2 O was dissolved in 10g of water, followed by immersion in 6g of gamma-Al 2 O 3 Evaporating the solvent in a water bath at 50 ℃, drying in an oven at 100 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the Re-La-based catalyst-17.
Example 13
Examples 1-12 and comparative examples 1-6 were prepared by dissolving hydroquinone-containing isopropanol solution and H 2 The application in the reaction for preparing 1,4-cyclohexanediol as raw materials.
Activation of the catalyst: GHSV =6000h in the reactor before catalyst use -1 In-situ reduction activation is carried out in a flow under the conditions: heating the mixture from room temperature to 500 ℃ at the temperature of 10 ℃/min under 0.1MPa, and keeping the temperature for 3h to obtain the activated inorganic oxide supported multi-metal catalyst.
The reaction conditions are as follows: at 90 ℃ and 1.5MPa 2 Hydroquinone =50:1 (molar ratio), hydroquinone solution flow rate 0.1mL/min, catalyst 0.5g, hydroquinone: solvent =1:9 (mass ratio).
Liquid phase product off-line analysis, DB-1701 capillary chromatography column, FID detector analysis hydroquinone and 1,4-cyclohexanediol content.
Using the inorganic oxide-supported multimetallic catalyst prepared in examples 1-12 and comparative examples 1-6 for the fixed bed and example 8 for the kettle reaction (19, 20), the hydroquinone conversion and 1,4-cyclohexanediol selectivity results are shown in Table 1.
TABLE 1 reaction results for the selective hydrogenation of hydroquinone to 1,4-cyclohexanediol
* The kettle type reaction conditions are as follows: 0.5g of hydroquinone, 0.05g of catalyst and 4.5g of solvent, 90 ℃,1MPa and 3h.
* Kettle type reaction conditions: 0.5g of hydroquinone, 0.05g of catalyst and 4.5g of solvent, 70 ℃,1MPa and 3h.
As can be seen from the comparison of the above results, the carrier is preferably gamma-Al 2 O 3 Re and a second metal species are used as a hydrogenation active center together, la species can better improve the hydrogenation stability of the catalyst than Ce species, tetraethyl orthosilicate and 3-propylaminotriethoxysilane can more effectively further improve the hydrogenation stability, and the space-time yield of the catalyst in a fixed bed embodiment can reach 1.25mol 1,4-cyclohexanediol /g Re /h。
FIG. 1 is a comparison of the reaction stability of 1,4-cyclohexanediol prepared by selective hydrogenation of hydroquinone in the presence of catalysts of some examples and comparative examples, and it can be seen that the catalyst of the present application has very excellent stability in the reaction process of 1,4-cyclohexanediol prepared by selective hydrogenation of hydroquinone in a fixed bed.
Example 14
The catalyst prepared in example 9 was used in this example for the hydrogenation of bisphenol a to hydrogenated bisphenol a.
Activation of the catalyst: GHSV =6000h in the reactor before catalyst use -1 Carrying out in-situ reduction activation in the flow under the conditions as follows: heating the mixture from room temperature to 500 ℃ at the temperature of 10 ℃/min under 0.1MPa, and keeping the temperature for 3h to obtain the activated inorganic oxide supported multi-metal catalyst.
The reaction conditions are as follows: at 90 ℃ and 1.5MPa 2 Bisphenol a =100:1 (molar ratio), bisphenol a solution flow rate of 0.1mL/min, catalyst of 0.5g, bisphenol a: solvent =1:9 (mass ratio).
The liquid phase product was analyzed off-line, DB-1701 capillary chromatography column, FID detector for bisphenol A and hydrogenated bisphenol A content.
TABLE 2 reaction results of selective hydrogenation of bisphenol A to hydrogenated bisphenol A
From the above results, it is understood that the catalyst can be used also in the production of hydrogenated bisphenol a by hydrogenation of bisphenol a, and exhibits excellent catalytic performance.
The invention realizes the preparation of 1,4-cyclohexanediol or bisphenol A by hydrogenation of the fixed bed hydroquinone with high activity, high selectivity and high stability under the low temperature condition (100 ℃), greatly simplifies the production process and is more suitable for industrial application.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The application of an inorganic oxide carrier-supported multi-metal catalyst in the reaction of preparing 1,4-cyclohexanediol by hydrogenating hydroquinone or preparing bisphenol A by hydrogenating bisphenol A is characterized in that the multi-metal catalyst consists of a main active component and a carrier, wherein the main active component is a first metal and a second metal or the first metal, the second metal and a third metal, and the first metal is Re; the second metal is one or more than two of Co, ni, fe and Cu; the third metal is one or more of La, ce and Y, and the carrier is an inorganic oxide carrier.
2. The use according to claim 1, wherein the multimetallic catalyst is modified by silylation.
3. The use of claim 1, wherein the first metal is present in an amount of 0.01 to 10.0wt% based on the weight of the catalyst; the content of the second metal is 0.01-30.0 wt% of the weight of the catalyst; the third metal content is 0.01-30.0 wt% of the catalyst weight.
4. Use according to claim 3, wherein the support is γ -Al 2 O 3 、TiO 2 Or ZnO or a combination of two or more thereof.
5. The use according to any one of claims 1 to 4, wherein the preparation process of the inorganic oxide support supported multimetallic catalyst comprises essentially the steps of:
dissolving precursors of a first metal and a second metal, or dissolving the precursors of the first metal, the second metal and a third metal in water, soaking the obtained solution on an inorganic oxide carrier in an equal volume or in an excessive amount, evaporating the solvent, drying, and roasting at 300-800 ℃ for 1-10 hours to obtain the catalyst;
or dissolving precursors of the first metal and the second metal, or dissolving the precursors of the first metal, the second metal and the third metal in water, soaking the obtained solution on an inorganic oxide carrier in an equal volume or in an excessive amount, evaporating the solvent, drying, adding the obtained catalyst into a silane species solution, maintaining the pH value at 4-9, stirring for 1-8 h, washing, filtering, drying, and roasting at 300-800 ℃ for 1-10 h to obtain the catalyst.
6. The use of claim 5, wherein the silane species in the silane species solution is one or more of methyltriethoxysilane, tetraethylorthosilicate, 3-propylaminotriethoxysilane, γ -mercaptopropyltriethoxysilane; the solvent is a mixed solution of an organic solvent and water, the organic solvent comprises methanol, ethanol, propanol, tetrahydrofuran and dimethyl sulfoxide, and the concentration of silane species is 0.001-1.0mol/L.
7. The use of claim 5, wherein the Re metal precursor is KReO 4 、Re 2 O 7 、NH 4 ReO 4 、HReO 4 、NaReO 4 One or more than two of them; the second metal precursor is Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 O、NiSO 4 ·7H 2 O、CoSO 4 ·7H 2 O、Fe(NO 3 ) 3 ·9H 2 O、FeCl 3 ·6H 2 O、Fe 2 (SO 4 ) 3 One or more than two of the above; the third metal species is La (NO) 3 ) 3 ·6H 2 O、LaCl 3 ·6H 2 O、La 2 (SO 4 ) 3 ·9H 2 O、Ce(NO 3 ) 3 ·6H 2 O、CeCl 3 、Ce 2 (SO 4 ) 3 ·8H 2 O、Y(NO 3 ) 3 ·6H 2 One or two or more of O.
8. The application of claim 1, wherein the main reactor adopted in the hydrogenation reaction process is a fixed bed reactor; the reaction temperature is 50-200 ℃, and the reaction pressure is 0.1-4.0 MPa.
9. The use according to claim 8, wherein the multi-metal catalyst is pre-reduction activated in situ in the reactor; the temperature of the pre-reduction activation process is 200-700 ℃, the pressure is 0.1-2.0 MPa, and the gas volume space velocity is 2000-8000h -1 。
10. The use of claim 9, wherein the hydrogenation reaction is carried out at a temperature of 50 to 100 ℃, a pressure of 0.1 to 3.0MPa, and a liquid volume space velocity of 0.1 to 500 hours -1 ，H 2 And hydroquinone or H 2 And bisphenol A in a molar ratio of 4000 to 3: the solvent of the hydroquinone solution or the bisphenol A solution is one or the combination of more than two of water, isopropanol, ethanol, methanol and acetone.
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| US3700742A (en) * | 1971-04-26 | 1972-10-24 | Universal Oil Prod Co | Aromatic hydrogenation process |
| JP2013010707A (en) * | 2011-06-29 | 2013-01-17 | Daicel Corp | Production method for polyol hydrogenolysis product |
| CN113292397A (en) * | 2021-06-02 | 2021-08-24 | 中国科学院大连化学物理研究所 | Composite oxide supported double transition metal catalyst for preparing 1, 4-cyclohexanediol by hydrogenation of hydroquinone under fixed bed catalysis |
| CN113680369A (en) * | 2021-09-10 | 2021-11-23 | 润泰化学（泰兴）有限公司 | Preparation method of bimetallic catalyst for preparing dioctyl phthalate by virtue of hydrogenation of dioctyl phthalate |
| CN114308035A (en) * | 2022-01-14 | 2022-04-12 | 浙江大学衢州研究院 | Hydrogenation catalyst for 1, 4-cyclohexanedicarboxylic acid, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3700742A (en) * | 1971-04-26 | 1972-10-24 | Universal Oil Prod Co | Aromatic hydrogenation process |
| JP2013010707A (en) * | 2011-06-29 | 2013-01-17 | Daicel Corp | Production method for polyol hydrogenolysis product |
| CN113292397A (en) * | 2021-06-02 | 2021-08-24 | 中国科学院大连化学物理研究所 | Composite oxide supported double transition metal catalyst for preparing 1, 4-cyclohexanediol by hydrogenation of hydroquinone under fixed bed catalysis |
| CN113680369A (en) * | 2021-09-10 | 2021-11-23 | 润泰化学（泰兴）有限公司 | Preparation method of bimetallic catalyst for preparing dioctyl phthalate by virtue of hydrogenation of dioctyl phthalate |
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