Double-non-noble-alloy supported catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of preparation of catalysts, in particular to a novel double-non-noble metal alloy supported catalyst and a preparation method and application thereof.The novel double-non-noble metal alloy supported catalyst is prepared with one of Fe, Ni, Cu and Co as a main active ingredient, the other one of the four metals as an auxiliary active ingredient and an oxide as a carrier, and forming a catalyst in which nano particles of two different metals are dispersed and loaded on the surface of the carrier. The effective combination of the two active sites is realized by accurately controlling the molar ratio of the main active metal to the auxiliary active metal. Under the action of the catalyst, H2 molecules are decomposed into hydrogen protons, and then the hydrogen protons are transferred to active sites, so that transfer of hydrogen atoms among substrate molecules is promoted, C = O double bonds are selectively hydrogenated to generate 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, and the reaction activity is remarkably improved; meanwhile, doping of the second metal not only facilitates activation of H2, but also enhances dispersity of the metal particles, so that selectivity of the product is improved.

Description

Technical Field

[0001] The invention relates to the technical field of catalyst preparation, and specifically discloses a double non-noble alloy supported catalyst and a preparation method and application thereof. Background Art

[0002] 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (CBDO) is a key high-performance polyester diol monomer. The symmetry of its molecular structure gives it the characteristics of cis-trans isomerism. CBDO plays an important role in the synthesis of copolyester products with high glass transition temperature, excellent transparency and strong impact resistance. These products are gradually replacing traditional polycarbonates and have become a hot topic in recent years.

[0003] The synthesis route of CBDO involves converting 2,2,4,4-tetramethyl-1,3-cyclobutanedione (TMCB) into CBDO through hydrogenation. However, the selective hydrogenation process of TMCB has encountered challenges in industrial application, such as harsh reaction conditions and insufficient catalyst activity.

[0004] At present, the catalysts used for catalytic hydrogenation of TMCB to prepare CBDO are mainly supported monometallic catalysts, in which the active metals are mostly precious metals such as Ru, Pd, Pt, Rh, Ir, etc., and the carriers include activated carbon, diatomaceous earth, silica-alumina mixtures, aluminates, etc. These precious metals are conducive to the adsorption of hydrogen due to their unfilled d orbitals and suitable Gibbs free energy, and show high activity in the reaction. However, the high cost of precious metals and the difficulty in controlling their selectivity limit their wide application.

[0005] In view of this, the development of a catalyst with high cost-effectiveness, strong activity and good selectivity is of great significance for the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Summary of the invention

[0006] In view of the problems of high cost and low catalytic activity of the catalyst for catalyzing the hydrogenation of TMCB to prepare CBDO in the prior art, a double non-precious alloy supported catalyst and its preparation method and application are provided. A catalyst in the form of nanoparticles of two different metals dispersed and supported on the surface of the carrier is formed by using one metal among Fe, Ni, Cu and Co as the main active component and another one of the four metals as the auxiliary active component, and oxide as the carrier. The catalyst can show good catalytic activity, low cost and easy to promote.

[0007] The specific technical solution of the invention is as follows:

[0008] A dual non-noble alloy supported catalyst, comprising nanoparticles of two different metals dispersed and supported on the surface of an oxide support;

[0009] The first metal is selected from one of iron, cobalt, copper and nickel;

[0010] The second metal is selected from one of iron, cobalt, copper and nickel;

[0011] The molar ratio of the first metal to the second metal is 1:0.02-1:0.08;

[0012] The first metal accounts for 3% to 15% of the catalyst by mass.

[0013] A catalyst with one of the metals Fe, Ni, Cu, and Co as the main active ingredient and another of the four metals as the auxiliary active ingredient, and oxide as the carrier, is formed in which nanoparticles of two different metals are dispersed and loaded on the surface of the carrier. The effective combination of the two active sites is achieved by precisely controlling the molar ratio of the main active metal to the auxiliary active metal. Under the action of this catalyst, H 2 The molecules are decomposed into hydrogen protons, which are then transferred to the active sites, promoting the transfer of hydrogen atoms between substrate molecules, thereby selectively hydrogenating the C=O double bond to generate 2,2,4,4-tetramethyl-1,3-cyclobutanediol, significantly improving the activity of the reaction; at the same time, the doping of the second metal is not only beneficial to the H 2 The activation also enhances the dispersion of metal particles, thereby improving the selectivity of the product.

[0014] Furthermore, the oxide support is TiO 2 、Al 2 O 3 , CuO, CeO 2 、MgO、ZrO 2 , Fe 2 O 3 、SiO 2 One of them.

[0015] Further, the molar ratio of the first metal to the second metal is 1:0.02-1:0.06. Preferably, the molar ratio of the first metal to the second metal is 1:0.02-1:0.04.

[0016] Furthermore, the first metal is cobalt and the second metal is copper. Specifically, when Co and Cu are doped, the size and valence of the metal particles can be changed. Cobalt is easy to lose electrons from Co 0 →Co 2+ , copper easily gets electrons from Cu 2+ →Cu 0 , which effectively regulated the electronic environment on the catalyst surface and successfully prepared a highly active dual non-precious metal catalyst. 0 and Co 0 Yes H 2The decomposed active sites promote the transfer of H atoms between adsorbed substrates, Co 2+ Contains oxygen vacancies, which is conducive to the adsorption and activation of carbonyl groups, thereby achieving highly selective hydrogenation of 2,2,4,4-tetramethyl-1,3-cyclobutanedione to produce 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Co2+ contains oxygen vacancies, which is conducive to the adsorption and activation of carbonyl groups. From the nature of electronic interaction, the electrons in the C=O double bond will be attracted by the positive charge of the oxygen vacancy and electron transfer will occur, so the oxygen vacancy can better adsorb the C=O double bond. This adsorption effect helps to promote the breaking of the C=O bond and the catalytic reaction, thereby improving the selectivity of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0017] Another object of the present invention is to provide a method for preparing the above-mentioned dual non-noble metal supported catalyst.

[0018] A method for preparing the above-mentioned dual non-noble metal supported catalyst comprises the following steps:

[0019] S1. Mix the metal salts of the two metals with deionized water, stir until the solid is dissolved, then add the oxide carrier C, and perform ultrasound;

[0020] S2, stirring, standing, and drying;

[0021] S3, the dried product is calcined, H 2 The catalyst is reduced under the action of NH4+ to obtain a double non-precious alloy supported catalyst.

[0022] The preparation method is simple to operate and easy to control, and can effectively ensure that the catalyst has good dispersibility.

[0023] Furthermore, in S1, the metal salt of the first metal is Fe 2 (SO 4 ) 3 6H 2 O, Fe(C 2 H 3 O 2 ) 2 ·4H 2 O. CoSO 4 7H 2 O、CoCl 2 6H 2 O.Ni(NO 3 ) 2 6H 2 O, Cu(NO 3 )·3H 2 O、Co(NO 3 ) 2 6H 2 O、CuSO4 ·5H 2 O、Cu(CH 3 COO 2 ·H 2 O、NiCl 2 6H 2 O.C 4 H 6 NiO 4 ·4H 2 O, Fe(NO 3 ) 2 9H 2 O, CuCl 2 ·2H 2 O、NiSO 4 6H 2 O, FeCl 3 6H 2 O、(CH 3 COO 2 Co·4H 2 One of O;

[0024] The metal salt of the second metal is Ni(NO 3 ) 2 6H 2 O, Cu(NO 3 )·3H 2 O、Co(NO 3 ) 2 6H 2 O、CuSO 4 ·5H 2 O、Cu(CH 3 COO 2 ·H 2 O、NiCl 2 6H 2 O.C 4 H 6 NiO 4 ·4H 2 O, Fe(NO 3 ) 2 9H 2 O, CuCl 2 ·2H 2 O、NiSO 4 6H 2 O, FeCl 3 6H 2 O, Fe 2 (SO 4 ) 3 6H 2 O, Fe(C 2 H 3 O2 ) 2 ·4H 2 O. CoSO 4 7H 2 O、CoCl 2 6H 2 O、(CH 3 COO 2 Co·4H 2 One of O.

[0025] Furthermore, in S2, the drying temperature is 60°C-80°C, and the drying time is 8h-12h.

[0026] Further, in S3, air roasting is performed in a muffle furnace, the roasting temperature is 300°C-800°C, the roasting time is 1-5h, and the heating rate of the muffle furnace is 2-5°C / min; H 2 The reduction treatment is carried out under the action of the catalyst, the reduction temperature is 300℃-800℃, the reduction time is 1-5h, and the heating rate of the tubular furnace is 2-5℃ / min.

[0027] Furthermore, in S3, the calcination temperature is 400-600°C, and the reduction temperature is 300-500°C.

[0028] Another object of the present invention is to protect the application of the above catalyst.

[0029] A catalyst prepared by the above-mentioned dual non-precious metal supported catalyst or the above-mentioned method for preparing the dual non-precious metal supported catalyst is used to catalyze 2,2,4,4-tetramethyl-1,3-cyclobutanediol to prepare 2,2,4,4-tetramethyl-1,3-cyclobutanedione.

[0030] After the catalytic reaction is completed, the catalyst and the product can be separated simply and efficiently by centrifugation, and the catalyst can be directly reused without post-processing. After testing, the catalytic performance of the catalyst did not decrease significantly after being reused five times, showing a good recycling effect.

[0031] A method for preparing 2,2,4,4-tetramethyl-1,3-cyclobutanediol comprises the following steps:

[0032] Step 1, adding 2,2,4,4-tetramethyl-1,3-cyclobutanedione, the dual non-precious metal supported catalyst as described in any one of claims 1 to 3, and an organic solvent into a high-temperature and high-pressure stainless steel reactor;

[0033] Step 2, using nitrogen to replace the air in the reactor 4-5 times, using hydrogen to replace the air in the reactor 3-4 times, and maintaining the hydrogen pressure at 1-5 MPa;

[0034] Step 3: heating and stirring to carry out catalytic reaction, cooling, and centrifuging to obtain 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0035] Furthermore, the mass ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanedione to the dual non-precious metal supported catalyst is 0.5-4:1.

[0036] Furthermore, the organic solvent is one of dichloromethane, ethanol, methanol, tetrahydrofuran, butyl acetate and ethyl acetate.

[0037] Furthermore, the temperature of the catalytic reaction is 80 to 150° C., and the time of the catalytic reaction is 120 to 240 minutes.

[0038] Furthermore, the stirring speed is 600-1000 rpm.

[0039] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0040] 1. The present invention relates to a novel double non-precious metal alloy supported catalyst, which uses one metal among Fe, Ni, Cu and Co as the main active component, and another one of the four metals as the auxiliary active component, and uses oxide as the carrier to form a catalyst in the form of nanoparticles of two different metals dispersed and supported on the surface of the carrier. The effective combination of the two active sites is achieved by precisely controlling the molar ratio of the main active metal to the auxiliary active metal. Under the action of this catalyst, H 2 The molecules are decomposed into hydrogen protons, which are then transferred to the active sites, promoting the transfer of hydrogen atoms between substrate molecules, thereby selectively hydrogenating the C=O double bond to generate 2,2,4,4-tetramethyl-1,3-cyclobutanediol, significantly improving the activity of the reaction. The doping of the second metal not only facilitates the H 2 The activation also enhances the dispersion of metal particles, thereby improving the selectivity of the product.

[0041] 2. The present invention provides a method for preparing a dual non-precious metal supported catalyst, which is simple to operate, easy to control, and can effectively ensure that the catalyst has good dispersibility.

[0042] 3. The application of the dual non-precious metal alloy supported catalyst of the present invention in catalyzing the hydrogenation of TMCB to prepare CBDO can be achieved by separating the catalyst from the product simply and efficiently by centrifugation after the catalytic reaction is completed. The catalyst can be directly reused without post-treatment. After testing, the catalytic performance of the catalyst did not decrease significantly after being reused 5 times, showing a good recycling effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1The figure is a synthetic route of the double non-precious alloy supported catalyst of the present invention.

[0044] Figure 2 This is the XRD spectrum of the double non-noble alloy supported catalyst of the present invention.

[0045] Figure 3 The double non-precious alloy supported catalyst Co / Al prepared in Comparative Example 1 2 O 3 EDS element diagram.

[0046] Figure 4 The double non-precious alloy supported catalyst CoCu / Al prepared in Example 1 2 O 3 EDS element map of -0.02.

[0047] Figure 5 The double non-precious alloy supported catalyst CoCu / Al prepared in Example 2 2 O 3 EDS element map of -0.04.

[0048] Figure 6 The double non-precious alloy supported catalyst CoCu / Al prepared in Example 3 2 O 3 EDS element map of -0.06. DETAILED DESCRIPTION

[0049] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail in the following embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0050] The embodiments of the present application are described in detail below. Examples of the embodiments are shown in the drawings, but unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of actually identical structures may be omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0051] Unless otherwise defined, all technical and scientific terms used in this application have the same meanings as those commonly understood by technicians in the technical field to which this application belongs; the terms used in this application are only for the purpose of describing specific embodiments and are not intended to limit this application; unless otherwise specified, the numerical values ​​of the parameters mentioned in this application can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the embodiments of this application).

[0052] The terms "including" and "having" in the specification and claims of the present application and any modifications thereof are open expressions, that is, including the contents specified in the present application but not excluding other contents.

[0053] In the description of the present application, "A and / or B" may include the case of A alone, the case of B alone, or any of the cases of A and B, where A and B are only used for examples and may be any technical feature connected by "and / or" in the present application.

[0054] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0055] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0056] The invention provides a double non-precious alloy supported catalyst, comprising nanoparticles of two different metals dispersed and supported on the surface of an oxide carrier; the first metal is selected from one of iron, cobalt, copper and nickel; the second metal is selected from one of iron, cobalt, copper and nickel; the molar ratio of the first metal to the second metal is 1:0.02-1:0.08; the mass of the first metal accounts for 3%-15% of the catalyst.

[0057] By precisely controlling the molar ratio of the main active metal to the auxiliary active metal, the two active sites are effectively combined. 2 The molecules are decomposed into hydrogen protons, which are then transferred to the active sites, promoting the transfer of hydrogen atoms between substrate molecules, thereby selectively hydrogenating the C=O double bond to generate 2,2,4,4-tetramethyl-1,3-cyclobutanediol, significantly improving the activity of the reaction. The doping of the second metal not only facilitates the H 2 The activation also enhances the dispersion of metal particles, thereby improving the selectivity of the product.

[0058] In some embodiments, the oxide support is TiO 2 、Al 2 O 3 , CuO, CeO 2 、MgO、ZrO 2 , Fe 2 O 3 、SiO 2 One of them.

[0059] Preferably, the molar ratio of the first metal to the second metal is 1:0.02-1:0.06. Preferably, the molar ratio of the first metal to the second metal is 1:0.02-1:0.04. Controlling the molar ratio of the two metals within a preferred range can better ensure the catalytic activity of the catalyst.

[0060] Furthermore, the first metal is cobalt and the second metal is copper. Studies have found that when the first metal is cobalt and the second metal is copper, the catalytic effect of the prepared double non-precious alloy supported catalyst is better.

[0061] The present invention provides a method for preparing the above-mentioned dual non-noble metal supported catalyst, such as Figure 1 As shown, the following steps are included:

[0062] S1. Mix the metal salts of the two metals with deionized water, stir until the solid is dissolved, then add the oxide carrier C, and perform ultrasound;

[0063] Preferably, in S1, the metal salt of the first metal is Fe 2 (SO 4 ) 3 6H 2 O, Fe(C 2 H 3 O 2 ) 2 ·4H 2 O. CoSO 4 7H 2 O、CoCl 2 6H 2 O.Ni(NO 3 ) 2 6H 2 O, Cu(NO 3 )·3H 2 O、Co(NO 3 ) 2 6H 2 O、CuSO 4 ·5H 2 O、Cu(CH 3 COO 2 ·H 2 O、NiCl 2 6H 2 O.C 4 H 6 NiO 4 ·4H 2 O, Fe(NO 3 ) 2 9H 2 O, CuCl 2 ·2H 2 O、NiSO4 6H 2 O, FeCl 3 6H 2 O、(CH 3 COO 2 Co·4H 2 One of O;

[0064] The metal salt of the second metal is Ni(NO 3 ) 2 6H 2 O, Cu(NO 3 )·3H 2 O、Co(NO 3 ) 2 6H 2 O、CuSO 4 ·5H 2 O、Cu(CH 3 COO 2 ·H 2 O、NiCl 2 6H 2 O.C 4 H 6 NiO 4 ·4H 2 O, Fe(NO 3 ) 2 9H 2 O, CuCl 2 ·2H 2 O、NiSO 4 6H 2 O, FeCl 3 6H 2 O, Fe 2 (SO 4 ) 3 6H 2 O, Fe(C 2 H 3 O 2 ) 2 ·4H 2 O. CoSO 4 7H 2 O、CoCl 2 6H 2 O、(CH 3 COO 2 Co·4H 2 One of O.

[0065] S2, stirring, standing, and drying; in some embodiments, the drying temperature is 60° C.-80° C., and the drying time is 8 h-12 h.

[0066] S3, the dried product is calcined, H 2 The catalyst is reduced under the action of NH4+ to obtain a double non-precious alloy supported catalyst.

[0067] In some embodiments, air calcination is performed in a muffle furnace at a temperature of 300°C-800°C, a calcination time of 1-5h, and a heating rate of 2-5°C / min in the muffle furnace; H 2 The reduction treatment is carried out under the action of the catalyst, the reduction temperature is 300℃-800℃, the reduction time is 1-5h, and the heating rate of the tubular furnace is 2-5℃ / min.

[0068] Preferably, in S3, the calcination temperature is 400-600° C., and the reduction temperature is 300-500° C. When the calcination temperature and the reduction temperature are controlled within the preferred range, the two metal nanoparticles in the prepared catalyst have better dispersion in the carrier and can exhibit better catalytic effect.

[0069] The present invention also provides an application of the above-mentioned dual non-precious metal supported catalyst or the catalyst prepared by the above-mentioned method for preparing the dual non-precious metal supported catalyst to catalyze 2,2,4,4-tetramethyl-1,3-cyclobutanediol in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanedione.

[0070] A method for preparing 2,2,4,4-tetramethyl-1,3-cyclobutanediol comprises the following steps:

[0071] Step 1, adding 2,2,4,4-tetramethyl-1,3-cyclobutanedione, the dual non-precious metal supported catalyst as described in any one of claims 1 to 3, and an organic solvent into a high-temperature and high-pressure stainless steel reactor;

[0072] In some embodiments, the mass ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanedione to the dual non-noble metal supported catalyst is 0.5-4:1.

[0073] In some embodiments, the organic solvent is one of dichloromethane, ethanol, methanol, tetrahydrofuran, butyl acetate, and ethyl acetate.

[0074] Step 2, using nitrogen to replace the air in the reactor 4-5 times, using hydrogen to replace the air in the reactor 3-4 times, and maintaining the hydrogen pressure at 1-5 MPa;

[0075] Step 3: heating and stirring to carry out catalytic reaction, cooling, and centrifuging to obtain 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0076] In some embodiments, the temperature of the catalytic reaction is 80-150° C., the time of the catalytic reaction is 120-240 min, and the stirring speed is 600-1000 rpm.

[0077] To this end, the present invention provides the following specific embodiments for further explanation.

[0078] Example 1-Example 4

[0079] S 1 , will Co(NO 3 ) 2 6H 2 O、CuSO 4 ·5H 2 O and deionized water were mixed in a 25.0 mL beaker and stirred until the solid was dissolved. 2 O 3 The carrier was ultrasonicated for 30 min, stirred at room temperature, and maintained for 12 h to obtain a corresponding mixed solution;

[0080] S 2 , stop the above stirring, let it stand overnight for 12 hours, and then place it in an oven at 80°C to dry for 6 hours;

[0081] S 3 , calcining the dried product in a muffle furnace, the calcination temperature is increased to 500°C at a rate of 2°C / min, and the calcination time is 3 hours; the obtained solid product is placed in a tubular furnace for reduction, the reduction temperature is increased to 400°C at a rate of 2°C / min, and the calcination time is 3 hours to obtain a catalyst.

[0082] The molar ratio of Co to Cu in the catalyst prepared in Example 1 is 1:0.02. By adjusting the amount of alumina carrier added, the mass proportion of metal cobalt in the catalyst is 10%, which is recorded as CoCu / Al 2 O 3 -0.02.

[0083] The molar ratio of Co to Cu in the catalyst prepared in Example 2 is 1:0.04. By adjusting the amount of alumina carrier added, the mass proportion of metal cobalt in the catalyst is 10%, which is recorded as CoCu / Al 2 O 3 -0.04.

[0084] The molar ratio of Co to Cu in the catalyst prepared in Example 3 is 1:0.06. By adjusting the amount of alumina carrier added, the mass proportion of metal cobalt in the catalyst is 10%, which is recorded as CoCu / Al 2 O 3 -0.06.

[0085] The molar ratio of Co to Cu in the catalyst prepared in Example 4 is 1:0.08. By adjusting the amount of alumina carrier added, the mass proportion of metal cobalt in the catalyst is 10%, which is recorded as CoCu / Al 2 O 3 -0.08.

[0086] Comparative Example 1

[0087] Comparative Example 1 does not add metallic copper, but only includes metallic cobalt, and the preparation method is the same as that of Example 1; by adjusting the amount of alumina carrier added, the mass proportion of metallic cobalt in the catalyst is 10%, which is recorded as Co / Al 2 O 3 .

[0088] Comparative Example 2

[0089] Comparative Example 2 was obtained by the same preparation method as Example 1.

[0090] The molar ratio of Co to Cu in the catalyst prepared in Comparative Example 2 is 1:0.01. By adjusting the amount of alumina carrier added, the mass proportion of metal cobalt in the catalyst is 10%, which is recorded as CoCu / Al 2 O 3 -0.01.

[0091] Comparative Example 3

[0092] Comparative Example 3 was obtained by the same preparation method as Example 1.

[0093] The molar ratio of Co to Cu in the catalyst prepared in Example 3 is 1:0.1. By adjusting the amount of alumina carrier added, the mass proportion of metal cobalt in the catalyst is 10%, which is recorded as CoCu / Al 2 O 3 -0.1.

[0094] Test 1

[0095] The catalytic activity of the catalysts prepared in Examples 1-4 and Comparative Examples 1-3 was tested.

[0096] Specific testing process:

[0097] 1.0g TMCB, 0.10g catalyst, 5mL butyl acetate and high temperature magnet were placed in a 50mL high temperature and high pressure stainless steel reactor, and the air in the reactor was replaced with nitrogen 4 times and hydrogen 3 times, the pressure in the high pressure reactor was maintained at 3MPa, the stirring speed was 600rpm, and the mixture was heated and stirred at 130℃ for 160min; after the reaction was completed, the mixture was allowed to stand and cool to room temperature. The product CBDO was obtained by centrifugal separation.

[0098] The conversion rate of TMCB and the yield of CBDO were calculated.

[0099] The calculation formulas for TMCB conversion and CBDO yield are as follows:

[0100]

[0101] The test results are shown in Table 1.

[0102] The catalyst was subjected to XRD and EDS tests, as shown in the following figure: Figure 2-6 shown.

[0103] Table 1

[0104] TMCB conversion rate (100%) CBDO yield (100%) Example 1 99.6 96.2 Example 2 82.7 90.4 Example 3 77.4 86.1 Example 4 72.5 82.9 Comparative Example 1 54.7 63.4 Comparative Example 2 63.5 69.6 Comparative Example 3 67.6 79.2

[0105] Example 5

[0106] S 1 , will Ni (NO 3 ) 2 6H 2 O、Co(NO 3 ) 2 6H 2 O and deionized water were mixed in a 25.0 mL beaker and stirred until the solid was dissolved. Then, TiO 2 The carrier was ultrasonicated for 30 min, stirred at room temperature, and maintained for 12 h to obtain a corresponding mixed solution;

[0107] S 2 , stop the above stirring, let it stand overnight for 12 hours, and then place it in an oven at 80°C to dry for 6 hours;

[0108] S 3 , calcining the dried product in a muffle furnace, the calcination temperature is increased to 300° C. at a rate of 2° C. / min, the calcination time is 3 h, the obtained solid product is placed in a tubular furnace for reduction, the reduction temperature is increased to 600° C. at a rate of 2° C. / min, the calcination time is 3 h, and a catalyst is obtained;

[0109] The molar ratio of Ni to Co in the catalyst prepared in Example 5 is 1:0.02. 2 The amount of carrier added, the mass proportion of metallic nickel in the catalyst is 5%.

[0110] Using the same catalyst activity test method as in Test 1, the TMCB conversion rate was measured to be 75.3% and the CBDO yield was 81.5%.

[0111] Example 6

[0112] S 1、CoSO 4 7H 2 O, Fe 2 (SO 4 ) 3 6H 2 O and deionized water were mixed in a 25.0 mL beaker and stirred until the solid was dissolved. 2 The carrier was ultrasonicated for 30 min, stirred at room temperature, and maintained for 12 h to obtain a corresponding mixed solution;

[0113] S 2 , stop the above stirring, let it stand overnight for 12 hours, and then place it in an oven at 80°C to dry for 6 hours;

[0114] S 3 , calcining the dried product in a muffle furnace, the calcination temperature is increased to 500° C. at a rate of 2° C. / min, the calcination time is 2 h, the obtained solid product is placed in a tubular furnace for reduction, the reduction temperature is increased to 800° C. at a rate of 2° C. / min, the calcination time is 4 h, to obtain a catalyst;

[0115] The molar ratio of Co to Fe in the catalyst prepared in Example 6 is 1:0.06. 2 The amount of carrier added, the mass proportion of metallic cobalt in the catalyst is 15%.

[0116] Using the same catalyst activity test method as in Test 1, the TMCB conversion rate was measured to be 70.4% and the CBDO yield was 74.1%.

[0117] Example 7

[0118] S 1 , CoCl 2 6H 2 O, Fe 2 (SO 4 ) 3 6H 2 O was mixed with deionized water in a 25.0 mL beaker, stirred until the solid was dissolved, and then MgO carrier was added, ultrasonicated for 30 min, stirred at room temperature, and maintained for 12 h to obtain the corresponding mixed solution;

[0119] S 2 , stop the above stirring, let it stand overnight for 12 hours, and then place it in an oven at 80°C to dry for 6 hours;

[0120] S 3, calcining the dried product in a muffle furnace, the calcination temperature is increased to 800° C. at a rate of 5° C. / min, the calcination time is 4 hours, the obtained solid product is placed in a tubular furnace for reduction, the reduction temperature is increased to 800° C. at a rate of 5° C. / min, the calcination time is 4 hours, and a catalyst is obtained;

[0121] The molar ratio of Co to Fe in the catalyst prepared in Example 7 is 1:0.03. By adjusting the amount of MgO carrier added, the mass proportion of metallic cobalt in the catalyst is 8%.

[0122] Using the same catalyst activity test method as in Test 1, the TMCB conversion rate was measured to be 82.8% and the CBDO yield was 86.5%.

[0123] Example 8

[0124] S 1 , will Ni (NO 3 ) 2 6H 2 O, Cu(NO 3 )·3H 2 O and deionized water were mixed in a 25.0 mL beaker and stirred until the solid was dissolved. 2 O 3 The carrier was ultrasonicated for 30 min, stirred at room temperature, and maintained for 12 h to obtain a corresponding mixed solution;

[0125] S 2 , stop the above stirring, let it stand overnight for 12 hours, and then place it in an oven at 80°C to dry for 6 hours;

[0126] S 3 , calcining the dried product in a muffle furnace, the calcination temperature is increased to 800° C. at a rate of 5° C. / min, the calcination time is 4 hours, the obtained solid product is placed in a tubular furnace for reduction, the reduction temperature is increased to 800° C. at a rate of 5° C. / min, the calcination time is 4 hours, and a catalyst is obtained;

[0127] The molar ratio of Ni to Cu in the catalyst prepared in Example 8 is 1:0.02. 2 O 3 The amount of carrier added, the mass proportion of metallic nickel in the catalyst is 4%.

[0128] Using the same catalyst activity test method as in Test 1, the TMCB conversion rate was measured to be 85.8% and the CBDO yield was 91.4%.

[0129] Example 9

[0130] The experimental conditions and steps were the same as those in Example 1, except that the catalyst was replaced by the catalyst recovered in Example 1. The experiment was repeated five times. After repeated use five times, the TMCB conversion rate was 98.6%, and the CBDO yield was 94.2%.

[0131] Comparative Example 4

[0132] S 1 、CoSO 4 7H 2 O、Zn(NO 3 ) 2 6H 2 O and deionized water were mixed in a 25.0 mL beaker and stirred until the solid was dissolved. 2 The carrier was ultrasonicated for 30 min, stirred at room temperature, and maintained for 12 h to obtain a corresponding mixed solution;

[0133] S 2 , stop the above stirring, let it stand overnight for 12 hours, and then place it in an oven at 80°C to dry for 6 hours;

[0134] S 3 , calcining the dried product in a muffle furnace, the calcination temperature is increased to 500° C. at a rate of 2° C. / min, the calcination time is 2 h, the obtained solid product is placed in a tubular furnace for reduction, the reduction temperature is increased to 800° C. at a rate of 2° C. / min, the calcination time is 4 h, to obtain a catalyst;

[0135] The molar ratio of Co to Zn in the catalyst prepared in Comparative Example 4 was 1:0.02. 2 The amount of carrier added, the mass proportion of metallic cobalt in the catalyst is 15%.

[0136] Using the same catalyst activity test method as Test 1, the TMCB conversion rate was measured to be 30.8% and the CBDO yield was 37.1%.

[0137] Comparative Example 5

[0138] S 1 、CoSO 4 7H 2 O、Ce(NO 3 ) 3 6H 2 O and deionized water were mixed in a 25.0 mL beaker and stirred until the solid was dissolved. 2 The carrier was ultrasonicated for 30 min, stirred at room temperature, and maintained for 12 h to obtain a corresponding mixed solution;

[0139] S 2, stop the above stirring, let it stand overnight for 12 hours, and then place it in an oven at 80°C to dry for 6 hours;

[0140] S 3 , calcining the dried product in a muffle furnace, the calcination temperature is increased to 500° C. at a rate of 2° C. / min, the calcination time is 2 h, the obtained solid product is placed in a tubular furnace for reduction, the reduction temperature is increased to 800° C. at a rate of 2° C. / min, the calcination time is 4 h, to obtain a catalyst;

[0141] The molar ratio of Co to Ce in the catalyst prepared in Comparative Example 5 was 1:0.02. 2 The amount of carrier added, the mass proportion of metallic cobalt in the catalyst is 15%.

[0142] Using the same catalyst activity test method as Test 1, the TMCB conversion rate was measured to be 35.8% and the CBDO yield was 42.5%.

[0143] Comparative Example 6

[0144] Comparative Example 6 adopts the same preparation method as Example 1. The molar ratio of Co and Cu in the prepared catalyst is 1:0.02. By adjusting the addition amount of the alumina carrier, the mass proportion of metal cobalt in the catalyst is 1%.

[0145] Using the same catalyst activity test method as in Test 1, the TMCB conversion rate was measured to be 42.9% and the CBDO yield was 48.2%.

[0146] Comparative Example 7

[0147] Comparative Example 7 adopts the same preparation method as Example 1. The molar ratio of Co and Cu in the prepared catalyst is 1:0.02. By adjusting the addition amount of the alumina carrier, the mass proportion of metallic cobalt in the catalyst is 20%.

[0148] Using the same catalyst activity test method as in Test 1, the TMCB conversion rate was measured to be 52.8% and the CBDO yield was 55.3%.

[0149] The novel double non-precious metal alloy supported catalyst of the present invention uses one metal among Fe, Ni, Cu and Co as the main active component and another one of the four metals as the auxiliary active component, and uses oxide as the carrier to form a catalyst in the form of nanoparticles of two different metals dispersed and supported on the surface of the carrier. The effective combination of the two active sites is achieved by precisely controlling the molar ratio of the main active metal to the auxiliary active metal. Under the action of this catalyst, H 2The molecules are decomposed into hydrogen protons, which are then transferred to the active sites, promoting the transfer of hydrogen atoms between substrate molecules, thereby selectively hydrogenating the C=O double bond to generate 2,2,4,4-tetramethyl-1,3-cyclobutanediol, significantly improving the activity of the reaction. The doping of the second metal not only facilitates the H 2 The activation also enhances the dispersion of metal particles, thereby improving the selectivity of the product.

[0150] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A double non-noble alloy supported catalyst, characterized in that: Nanoparticles of two different metals are dispersed and loaded on the surface of an oxide support; The first metal is selected from one of iron, cobalt, copper and nickel; The second metal is selected from one of iron, cobalt, copper and nickel; The molar ratio of the first metal to the second metal is 1:0.02-1:0.08; The first metal accounts for 3% to 15% of the catalyst by mass.

2. The double non-noble alloy supported catalyst according to claim 1, characterized in that: The oxide carrier is one of TiO2, Al2O3, CuO, CeO2, MgO, ZrO2, Fe2O3, and SiO2.

3. The double non-noble alloy supported catalyst according to claim 1, characterized in that: The molar ratio of the first metal to the second metal is 1:0.02-1:0.

06.

4. The double non-noble alloy supported catalyst according to any one of claims 1 to 3, characterized in that: The first metal is cobalt and the second metal is copper.

5. A method for preparing a dual non-noble metal supported catalyst as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: S1. Mix the metal salts of the two metals with deionized water, stir until the solid is dissolved, then add the oxide carrier C, and perform ultrasound; S2, stirring, standing, and drying; S3. The dried product is sequentially calcined and reduced under the action of H2 to obtain a double non-precious alloy supported catalyst.

6. The method for preparing a dual non-noble metal supported catalyst according to claim 5, characterized in that: In S1, the metal salt of the first metal is one of Fe2(SO4)3·6H2O, Fe(C2H3O2)2·4H2O, CoSO4·7H2O, CoCl2·6H2O, Ni(NO3)2·6H2O, Cu(NO3)·3H2O, Co(NO3)2·6H2O, CuSO4·5H2O, Cu(CH3COO)2·H2O, NiCl2·6H2O, C4H6NiO4·4H2O, Fe(NO3)2·9H2O, CuCl2·2H2O, NiSO4·6H2O, FeCl3·6H2O, (CH3COO)2Co·4H2O; The metal salt of the second metal is one of Ni(NO3)2·6H2O, Cu(NO3)·3H2O, Co(NO3)2·6H2O, CuSO4·5H2O, Cu(CH3COO)2·H2O, NiCl2·6H2O, C4H6NiO4·4H2O, Fe(NO3)2·9H2O, CuCl2·2H2O, NiSO4·6H2O, FeCl3·6H2O, Fe2(SO4)3·6H2O, Fe(C2H3O2)2·4H2O, CoSO4·7H2O, CoCl2·6H2O, and (CH3COO)2Co·4H2O.

7. The method for preparing a dual non-noble metal supported catalyst according to claim 5, characterized in that: In S2, the drying temperature is 60°C-80°C, and the drying time is 8h-12h.

8. The method for preparing a dual non-noble metal supported catalyst according to any one of claims 5 to 7, characterized in that: In S3, air roasting is carried out in a muffle furnace, the roasting temperature is 300℃-800℃, the roasting time is 1-5h, and the heating rate of the muffle furnace is 2-5℃ / min; reduction treatment is carried out in a tubular furnace under the action of H2, the reduction temperature is 300℃-800℃, the reduction time is 1-5h, and the heating rate of the tubular furnace is 2-5℃ / min.

9. Use of a catalyst prepared by the dual non-precious metal supported catalyst as claimed in any one of claims 1 to 4 or the method for preparing the dual non-precious metal supported catalyst as claimed in any one of claims 5 to 8 to catalyze 2,2,4,4-tetramethyl-1,3-cyclobutanediol in the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanedione.

10. A method for preparing 2,2,4,4-tetramethyl-1,3-cyclobutanediol, characterized in that: The following steps are involved: Step 1, adding 2,2,4,4-tetramethyl-1,3-cyclobutanedione, the dual non-precious metal supported catalyst as described in any one of claims 1 to 4, and an organic solvent into a high-temperature and high-pressure stainless steel reactor; Step 2, using nitrogen to replace the air in the reactor 4-5 times, using hydrogen to replace the air in the reactor 3-4 times, and maintaining the hydrogen pressure at 1-5 MPa; Step 3: heating and stirring to carry out catalytic reaction, cooling, and centrifuging to obtain 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

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