CN114570373A - Copper-silicon catalyst, preparation method and application in preparing cyclohexanone by dehydrogenation - Google Patents

Copper-silicon catalyst, preparation method and application in preparing cyclohexanone by dehydrogenation Download PDF

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CN114570373A
CN114570373A CN202011393260.1A CN202011393260A CN114570373A CN 114570373 A CN114570373 A CN 114570373A CN 202011393260 A CN202011393260 A CN 202011393260A CN 114570373 A CN114570373 A CN 114570373A
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copper
silicon
catalyst
oxide
precursor
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程帅
国海光
孙海霞
孙兵
安爱生
王林敏
刘洋洋
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Shanghai Sunchem New Materials Technology Co ltd
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Abstract

The invention provides a copper-silicon catalyst, which comprises an active component, a composite carrier and an auxiliary agent. In the copper-silicon catalyst, the composite carrier consists of silicon oxide and zirconium oxide, which is beneficial to improving the dispersibility and activity of the active component through strong interaction between the zirconium oxide and the active component, the content of the active component is controlled to be 32-45%, the content of the composite carrier is 45-70%, the content of the auxiliary agent is 1-5%, and the auxiliary agent is selected to be any one of alkali metal oxide and alkaline earth metal oxide, so that good synergistic effect is beneficial to being realized among the composite carrier, the active component and the auxiliary agent, the cyclohexene content in the product can be effectively controlled to be not higher than 31ppm, the phenol content is not higher than 62ppm, and the copper-silicon catalyst has good anti-carbon deposition performance even if the copper-silicon catalyst is continuously operated for 836 hours. The invention also provides a preparation method of the copper-silicon catalyst and application of the copper-silicon catalyst in preparation of cyclohexanone by cyclohexanol dehydrogenation.

Description

Copper-silicon catalyst, preparation method and application in preparing cyclohexanone by dehydrogenation
Technical Field
The invention relates to the field of catalysis, in particular to a copper-silicon catalyst, a preparation method and application in preparing cyclohexanone by dehydrogenation.
Background
Cyclohexanone is an important organic chemical raw material, and downstream products of the cyclohexanone are mainly caprolactam and adipic acid, and can be respectively applied to the production of nylon-6 and nylon-66. Cyclohexanone is also an excellent industrial solvent, can dissolve various substances such as nitrocellulose, paint, dye, pesticide and the like, and has good application value.
In the prior art, cyclohexanone is prepared by adopting a cyclohexanol dehydrogenation method, and used catalysts comprise a zinc-based catalyst and a copper-based catalyst. The zinc catalyst has high reaction activity, but the required reaction temperature is usually more than 350 ℃, so that the energy consumption is increased, the selectivity of the product is poor, and a large amount of byproducts are easily generated, thereby affecting the quality of the product.
In addition, with the increase of the reaction time, the organic matters are continuously condensed and dehydrogenated on the surface of the catalyst, so that carbon deposit covering the surface of the catalyst is formed, and the activity of the catalyst is obviously reduced. Therefore, there is a need to develop a catalyst having good anti-carbon properties to extend the catalyst life.
Chinese patent No. CN102527385B discloses a catalyst composed of cuprous oxide and magnesium oxide. The catalyst is applied to normal-pressure gas-phase dehydrogenation of cyclohexanol at the reaction temperature of 250 ℃ to prepare cyclohexanone, so that the conversion rate of cyclohexanol can reach 86.2%, and the selectivity of cyclohexanone is about 100%. However, the reaction time for preparing cyclohexanone by atmospheric pressure gas phase dehydrogenation of cyclohexanol disclosed in the invention is 2 hours, and the carbon deposition resistance of the catalyst under continuous long-time production operation is not disclosed.
Therefore, there is a need to develop a novel copper-silicon based catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and avoiding the above problems of the prior art.
Disclosure of Invention
The invention aims to provide a copper-silicon catalyst, a preparation method of the copper-silicon catalyst and application of the copper-silicon catalyst in preparation of cyclohexanone by cyclohexanol dehydrogenation, on the basis of ensuring that the conversion rate of cyclohexanol and the selectivity of cyclohexanone meet the average level in the industry, the copper-silicon catalyst can effectively control the cyclohexene content in a product to be not higher than 31ppm and the phenol content to be not higher than 62ppm, and has good anti-carbon deposition performance even if the copper-silicon catalyst is continuously operated for 836 hours.
In order to achieve the purpose, the copper-silicon catalyst comprises an active component, a composite carrier and an auxiliary agent; the copper-silicon catalyst comprises, by mass, 32-45% of the active ingredient, 45-70% of the composite carrier and 1-5% of the auxiliary agent; the active component is copper oxide, the composite carrier is composed of silicon oxide and zirconium oxide, and the auxiliary agent is any one of alkali metal oxide and alkaline earth metal oxide.
The copper-silicon catalyst has the beneficial effects that: the composite carrier in the copper-silicon catalyst consists of silicon oxide and zirconium oxide, and because the zirconium oxide has the semiconductor characteristic, each zirconium element can be coordinated with more than 7 oxygen elements, so that oxygen vacancies are easily generated, the dispersibility and the activity of the active components can be improved by the strong interaction between the zirconium oxide and the active components, the content of the active components is controlled to be 32-45 percent in a combined manner, the content of the composite carrier is 45-70 percent, the content of the auxiliary agent is 1-5 percent, and the auxiliary agent is selected to be any one of alkali metal oxide and alkaline earth metal oxide, so that the good synergistic effect can be realized among the composite carrier, the active components and the auxiliary agent, and the cyclohexene content in the product can be effectively controlled to be not more than 31ppm on the basis of ensuring that the conversion rate of cyclohexanol and the selectivity of cyclohexanone meet the average level in the industry, the phenol content is not higher than 62ppm and has good carbon deposition resistance even if the continuous operation is carried out for 836 hours.
Preferably, the copper oxide is cuprous oxide, the alkali metal oxide is any one of sodium oxide and potassium oxide, and the alkaline earth metal oxide is any one of calcium oxide, magnesium oxide, strontium oxide and barium oxide. The beneficial effects are that: is beneficial to improving the dehydrogenation activity of the copper-silicon catalyst and reducing the deep hydrogenation activity of the cyclohexanone, thereby weakening the reaction degree of side reaction.
Preferably, the specific surface area of the copper-silicon catalyst is 205-285 square meters per gram, the pore volume is 0.25-0.65 cubic meters per gram, and the average pore diameter is 4.0-10.5 nanometers. The beneficial effects are that: suitable surface properties are provided to facilitate good dispersion of the active ingredient.
Preferably, the copper-silicon catalyst is in a columnar shape, the average lateral pressure strength of the columnar copper-silicon catalyst is not less than 200 newtons, and the content of the forming agent is not more than 6% by mass of the copper-silicon catalyst. The beneficial effects are that: the method is favorable for preventing the copper-silicon catalyst from being broken in the subsequent application process, thereby avoiding the fine copper-silicon catalyst generated by breaking from being entrained in the product.
The preparation method of the copper-silicon catalyst comprises the following steps:
s0: providing a primary carrier, a cuprammonium solution and a mixed solution, wherein the primary carrier contains a silicon precursor and a zirconium precursor loaded on the surface of the silicon precursor, and the mixed solution contains a precursor of the auxiliary agent;
s1: sequentially carrying out first dipping treatment, ammonia evaporation treatment and washing and drying treatment on the original carrier through the copper ammonia solution, so that copper ions in the copper ammonia solution are loaded on the surface of the original carrier to obtain an intermediate precursor;
s2: carrying out second dipping treatment on the intermediate precursor through the mixed solution, and then sequentially carrying out drying treatment and roasting treatment on the obtained wet carrier;
in the copper ammonia solution, the molar ratio of ammonia to copper is 2.5-3.5, the mass ratio of the original carrier to copper in the copper ammonia solution is 1.5-2.0, and the mass ratio of the intermediate precursor to the precursor of the auxiliary agent is 15-60.
The copper-silicon catalyst has the beneficial effects that: adopting an original carrier containing a silicon precursor and a zirconium precursor loaded on the surface of the silicon precursor as raw materials, introducing zirconium oxide into the intermediate precursor obtained after the step S1, wherein the zirconium oxide has semiconductor characteristics, each zirconium element can be coordinated with more than 7 oxygen elements, so that oxygen vacancies are easily generated, and the dispersibility and activity of the active components are improved by virtue of strong interaction between the zirconium oxide and the active components, combining the ammonia evaporation treatment under the premise that the molar ratio of ammonia to copper in the copper ammonia solution is controlled to be 2.5-3.5 in the step S1, the mass ratio of the original carrier to copper in the copper ammonia solution is controlled to be 1.5-2.0, and the mass ratio of the intermediate precursor to the auxiliary agent is controlled to be 15-60 in the impregnation treatment of the step S2 to regulate the content of each component in the active components, the method is favorable for realizing a good synergistic effect among the composite carrier, the active component and the auxiliary agent, so that the cyclohexene content in the product can be effectively controlled to be not higher than 31ppm, the phenol content in the product to be not higher than 62ppm on the basis of ensuring that the conversion rate of cyclohexanol and the selectivity of cyclohexanone meet the average level in the industry, and the product has good carbon deposition resistance even if the product is continuously operated for 836 hours.
Preferably, the pH of the copper ammonia solution is 10 to 11, the valence state of copper in the copper ammonia solution is positive, in step S1, the temperature of the ammonia evaporation treatment is 70 to 90 ℃, the pressure is 0.06 to 0.1 mpa, the pH of steam is detected during the ammonia evaporation treatment, and the ammonia evaporation treatment is stopped when the pH of the steam is 7.0 to 7.5. The beneficial effects are that: the active component is cuprous oxide, which is beneficial to improving the dehydrogenation activity of the copper-silicon catalyst and reducing the deep hydrogenation activity of cyclohexanone, thereby weakening the reaction degree of side reaction.
Further preferably, a copper precursor, an ammonium precipitant and ammonia water are used to prepare an original copper ammonia solution, and the original copper ammonia solution is subjected to reduction treatment for 4 to 18 hours by hydrogen gas under an inert atmosphere to obtain the copper ammonia solution.
Further preferably, the copper precursor includes at least one of metallic copper, copper oxide, copper nitrate and copper acetate, and the ammonium precipitant is an alkaline substance containing ammonia or a salt substance containing ammonium ions.
Preferably, after the step S2 is finished, a forming agent is mixed with the catalyst powder obtained by the calcination treatment and then is tableted to obtain the columnar copper-silicon catalyst, wherein the forming agent accounts for not more than 6% of the columnar copper-silicon catalyst by mass. The beneficial effects are that: the method is favorable for preventing the copper-silicon catalyst from being broken in the subsequent application process, thereby avoiding the fine copper-silicon catalyst generated by breaking from being entrained in the product.
Preferably, the silicon precursor is silicon powder, the particle size of the silicon powder is 5-30 microns, the specific surface area is 100-400 square meters per gram, the zirconium precursor is at least one of zirconium nitrate, zirconium acetate and zirconium chloride, the zirconium precursor is loaded on the surface of the silicon precursor through a precipitator, and the precipitator is an ammonia-containing alkaline substance or a salt substance containing ammonium ions. The beneficial effects are that: the zirconium precursor can be well dispersed and loaded on the surface of the silicon precursor.
Preferably, the precursor of the auxiliary agent is any one of alkali metal water-soluble salt and alkaline earth metal water-soluble salt, the alkali metal element in the alkali metal water-soluble salt is any one of sodium and potassium, and the alkaline earth metal element in the alkaline earth metal water-soluble salt is any one of calcium, magnesium, strontium and barium. The beneficial effects are that: facilitating good dispersion and loading of the at least one metal on the intermediate precursor.
The application of the copper-silicon catalyst in preparing cyclohexanone by dehydrogenation comprises the following steps: placing the copper-silicon catalyst in a bed layer of a fixed bed reactor, carrying out catalyst reduction through reducing gas to form a pretreated copper-silicon catalyst, and enabling gaseous reactant to flow through the pretreated copper-silicon catalyst to carry out normal-pressure dehydrogenation reaction; the temperature of the atmospheric dehydrogenation reaction is 190-230 ℃, the gaseous reactant is gaseous cyclohexanol, and the volume space velocity of the cyclohexanol is 0.6-3 hours-1。
The application of the invention has the beneficial effects that: because the composite carrier in the copper-silicon catalyst consists of silicon oxide and zirconium oxide, and the zirconium oxide has the semiconductor characteristic, each zirconium element can be coordinated with more than 7 oxygen elements, so that oxygen vacancies are easily generated, the dispersibility and the activity of the active component can be improved by the strong interaction between the zirconium oxide and the active component, the content of the active component is controlled to be 32-45 percent, the content of the composite carrier is 45-70 percent, the content of the auxiliary agent is 1-5 percent, and the auxiliary agent is selected to be any one of alkali metal oxide and alkaline earth metal oxide, so that the good synergistic effect can be realized among the composite carrier, the active component and the auxiliary agent, the copper-silicon catalyst is applied to preparing cyclohexanone by dehydrogenating cyclohexanol, and the temperature of atmospheric pressure dehydrogenation reaction is controlled to be 190-230 ℃, the gaseous reactant is gaseous cyclohexanol, and the volume space velocity of the cyclohexanol is 0.6-3 hours-1Therefore, on the basis of ensuring that the conversion rate of cyclohexanol and the selectivity of cyclohexanone meet the average level in the industry, the cyclohexene content in the product can be effectively controlled to be not higher than 31ppm, the phenol content in the product is not higher than 62ppm, and the product still has good carbon deposition resistance even if the product is continuously operated for 836 hours.
Preferably, the reducing gas consists of hydrogen and inert atmosphere, the volume percentage of the hydrogen in the reducing gas is not less than 1%, the temperature for reducing the catalyst is 240-300 ℃, and the time duration is 2-24 hours. The beneficial effects are that: helps to activate the copper silicon based catalyst to enhance dehydrogenation activity.
Drawings
FIG. 1 is a flow chart of a method for preparing a copper-silicon based catalyst according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. As used herein, the word "comprising" and similar words are intended to mean that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items.
Aiming at the problems in the prior art, the embodiment of the invention provides a copper-silicon catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, wherein the copper-silicon catalyst comprises an active ingredient, a composite carrier and an auxiliary agent.
The room temperature in the embodiment of the invention refers to the ambient temperature of 17-35 ℃, and the normal pressure refers to 1 standard atmospheric pressure. The particle size refers to the diameter of a sphere with the same behavior as the particle size to be measured, namely the equivalent diameter. The specific surface area, the pore volume and the average pore diameter are all obtained by a BET test method, and the specific test method is a conventional technical means of a person skilled in the art and is not described herein in detail.
In the embodiment of the invention, the content of the active component is 32-45%, the content of the composite carrier is 45-70%, and the content of the auxiliary agent is 1-5% by mass percentage of the copper-silicon catalyst.
Furthermore, the specific surface area of the copper-silicon catalyst is 205-285 square meters/gram, the pore volume is 0.25-0.65 cubic meters/gram, and the average pore diameter is 4.0-10.5 nanometers.
In the embodiment of the invention, the active component is copper oxide, the composite carrier is composed of silicon oxide and zirconium oxide, and the auxiliary agent is composed of any one of alkali metal oxide and alkaline earth metal oxide.
In some embodiments of the present invention, the alkali metal oxide is any one of sodium oxide and potassium oxide, and the alkaline earth metal oxide is any one of calcium oxide, magnesium oxide, strontium oxide, and barium oxide.
In some embodiments of the invention, the copper oxide is cuprous oxide with a molecular formula of Cu2O。
In some embodiments of the present invention, the silicon oxide is silicon dioxide with a molecular formula of SiO2。
In some embodiments of the invention, the zirconium oxide is zirconium dioxide having the formula ZrO2。
In some embodiments of the invention, the sodium oxide is sodium oxide with the molecular formula Na2O。
In some embodiments of the invention, the potassium oxide is potassium oxide and has the formula K2O。
In some embodiments of the invention, the calcium oxide is calcium oxide and the molecular formula is CaO.
In some embodiments of the invention, the magnesium oxide is magnesium oxide and has the molecular formula of MgO.
In some embodiments of the present invention, the strontium oxide is strontium oxide and the molecular formula is SrO.
Referring to fig. 1, the preparation method of the copper-silicon based catalyst according to the embodiment of the present invention includes:
s0: providing a primary carrier, a cuprammonium solution and a mixed solution, wherein the primary carrier contains a silicon precursor and a zirconium precursor loaded on the surface of the silicon precursor, and the mixed solution contains a precursor of the auxiliary agent;
s1: sequentially carrying out first dipping treatment, ammonia evaporation treatment and washing and drying treatment on the original carrier through the copper ammonia solution, so that copper ions in the copper ammonia solution are loaded on the surface of the original carrier to obtain an intermediate precursor;
s2: and carrying out second dipping treatment on the intermediate precursor through the mixed solution, and then sequentially carrying out drying treatment and roasting treatment on the obtained wet carrier.
In step S0 of some embodiments of the present invention, the original support is prepared by performing a solid phase synthesis reaction on a silicon precursor, a zirconium precursor and a precipitating agent.
In some embodiments of the invention, the silicon precursor is derived from a silicon-containing material, and the silicon-containing material is at least one of silica sol, ethyl orthosilicate and water glass; the zirconium precursor is at least one of zirconium nitrate, zirconium acetate and zirconium chloride, and the precipitator is an ammonia-containing alkaline substance or a salt substance containing ammonium ions.
In embodiments 1 to 6 of the present invention, silicon powder is obtained as a silicon precursor after drying the silicon-containing substance at 120 ℃ for 3 to 5 hours at 100-.
Specifically, the particle size of the silicon powder is 5-30 microns, and the specific surface area is 100-400 square meters per gram.
The specific surface area, pore volume and average pore diameter of the silicon powder used in examples 1 to 6 of the present invention were equivalent to the corresponding specific surface area, pore volume and average pore diameter of the copper-silicon-based catalyst obtained by the method for preparing the copper-silicon-based catalyst.
In the solid-phase synthesis reaction of embodiments 1 to 6 of the present invention, the silicon-containing substances used are silica sol with a mass concentration of 30%, the zirconium precursors used are zirconium nitrate pentahydrate, and the precipitants used are ammonium carbonate.
The volume of silica sol, the mass of zirconium nitrate pentahydrate, and the mass of ammonium carbonate used in examples 1-6 of the present invention are shown in Table 1.
TABLE 1
Figure BDA0002813462700000081
Figure BDA0002813462700000091
In embodiments 1 to 6 of the present invention, after the solid phase synthesis reaction is completed, the obtained product is dried at 110 ℃ for 12 hours, and then is baked in a muffle furnace at 550 ℃ for 6 hours, so as to obtain the original carrier.
In step S0 of some embodiments of the present invention, the ammonia to copper molar ratio in the copper ammonia solution is 2.5-3.5. The ammonia is hydrated ammonia (NH)3.H2NH in O)3。
In the copper ammonia solutions of the embodiments 1 to 6 of the present invention, the molar ratio of ammonia to copper is 3, and the pH values of the copper ammonia solutions are 10 to 11.
In step S0 of some embodiments of the present invention, an original cuprammonia solution is prepared by using a copper precursor, an ammonium precipitant, and ammonia water, and the original cuprammonia solution is subjected to a reduction treatment for 4 to 18 hours by using hydrogen gas under an inert atmosphere to obtain the cuprammonia solution.
In some embodiments of the present invention, the copper precursor comprises at least one of copper metal, copper oxide, copper nitrate and copper acetate, and the ammonium precipitant is an alkaline substance containing ammonia or a salt substance containing ammonium ions.
In embodiments 1 to 6 of the present invention, the reduction treatment specifically includes: putting a copper precursor, an ammonium precipitator and water into a reaction kettle, and adding ammonia water to form a copper ammonia precursor solution after uniformly dissolving; introducing an inert atmosphere into the reaction kettle and stirring for 6 hours at room temperature; and then, switching the inert atmosphere to hydrogen, and continuing stirring and reacting for 10 hours until substances in the reaction kettle are in a solution state to complete the reduction reaction, so that the valence state of copper in the copper ammonia solution is positive valence.
Specifically, the copper precursors used in examples 1 to 6 of the present invention are copper powder and copper nitrate trihydrate, the ammonium precipitants used are ammonium bicarbonate, the ammonia water used is concentrated ammonia water with a mass concentration of 25%, and the pH values of the copper ammonia precursors are both 10.
The mass of copper powder, the mass of copper nitrate trihydrate, the mass of ammonium bicarbonate and the volume of concentrated ammonia used in examples 1-6 of the present invention are shown in Table 2.
TABLE 2
Figure BDA0002813462700000101
Figure BDA0002813462700000111
In step S0 of some embodiments of the present invention, the mixed solution is a solution prepared by a precursor of the auxiliary agent and water.
Specifically, the precursor of the auxiliary agent is any one of alkali metal water-soluble salt and alkaline earth metal water-soluble salt, the alkali metal element in the alkali metal water-soluble salt is any one of sodium and potassium, and the alkaline earth metal element in the alkaline earth metal water-soluble salt is any one of calcium, magnesium, strontium and barium.
In the mixed liquid of examples 1-6 of the present invention, the types and the masses of the precursor of the auxiliary agent, and the volume of water are shown in table 3.
TABLE 3
Figure BDA0002813462700000112
In step S1 of some embodiments of the present invention, the mass ratio of the raw carrier to the copper in the cuprammonium solution is 1.5-2.0.
In examples 1 to 6 of the present invention, the mass ratios of the raw support to copper in the cuprammonia solution were 1.6, 1.4, 1.8, and 1.7, respectively.
In some embodiments of the invention, the first immersion treatment is not less than 4 hours long.
In embodiments 1 to 6 of the present invention, after the raw carrier is added to the copper ammonia solution in step S0, the raw carrier is stirred and immersed at 40 degrees celsius for 4 hours to complete the first immersion treatment.
Specifically, the masses of the primary carriers added in examples 1 to 6 of the present invention were 168.0 g, 164.1 g, 159.6 g, 155.7 g, 170.7 g and 168.6 g, respectively.
Further, after the dipping treatment is completed, the ammonia evaporation treatment is performed on the mixture obtained after the stirring and dipping at 80 ℃ and a vacuum degree of 0.08 MPa. And detecting the pH value of the steam in the ammonia distillation process, and stopping the ammonia distillation process when the pH value of the steam is 7.0-7.5.
In embodiments 1 to 6 of the present invention, after the ammonia evaporation treatment is completed, the carrier obtained after the ammonia evaporation treatment is washed with deionized water and then dried at 120 ℃ for 12 hours to remove free water, so that the washing and drying treatment is completed, and the intermediate precursor is obtained.
In step S2 of some embodiments of the present invention, the mass ratio of the intermediate precursor to the precursor of the assistant agent is 15-60.
In the step S2 of some embodiments of the present invention, the duration of the second dipping process is not less than 5 hours.
Specifically, in embodiments 1 to 6 of the present invention, the mixed solution obtained in step S0 is added dropwise to the intermediate precursor, and then stirred and immersed for 5 hours to complete the second immersion treatment.
Further, after the second impregnation treatment is completed, the copper-silicon catalyst is obtained by drying at 110 ℃ for 12 hours and then roasting at 400 ℃ for 6 hours.
In some embodiments of the present invention, since the copper-silicon-based catalyst is in a granular form, after the step S2 is completed, the forming agent and the catalyst powder obtained by the calcination treatment are mixed and then subjected to a tabletting treatment to obtain a columnar copper-silicon-based catalyst, which is beneficial to preventing the copper-silicon-based catalyst from being broken in a subsequent application process, so as to prevent a fine copper-silicon-based catalyst generated by breaking from being entrained in a product. The tabletting process is a conventional technique for those skilled in the art and will not be described herein.
Further, the forming agent accounts for not more than 6% of the columnar copper-silicon catalyst by mass.
In some embodiments of the invention, the forming agent accounts for 4-6% of the columnar copper-silicon catalyst by mass.
Specifically, the forming agent is graphite and water, the graphite accounts for 2-4% by mass of the columnar copper-silicon catalyst, and the water accounts for 1-2% by mass of the columnar copper-silicon catalyst.
In the embodiments 1 to 6 of the present invention, the molding agent is graphite and water.
In examples 1 to 6 of the present invention, the copper silicon catalysts obtained by the tableting treatment were all cylindrical in shape, and the diameter and height were 5 mm and 3 mm, respectively.
More specifically, the active components in the copper-silicon catalyst are cuprous oxide, and the composite carrier is composed of silicon dioxide and zirconium dioxide.
The contents of cuprous oxide, silicon dioxide, zirconium dioxide, auxiliary agent, water and graphite, the types of auxiliary agent, and the specific surface area, pore volume and average pore diameter of the copper-silicon-based catalyst in examples 1 to 6 of the present invention are shown in table 4. The units of specific surface area, pore volume and average pore diameter are square meter/gram, cubic meter/gram and nanometer, respectively.
TABLE 4
Figure BDA0002813462700000131
Figure BDA0002813462700000141
The average lateral pressure strength of the cylindrical copper-silicon catalysts of examples 1 to 6 of the present invention is not less than 200 newtons, which is advantageous for preventing the copper-silicon catalysts from being broken easily and maintaining a certain mechanical strength in the subsequent application process.
Specifically, the average lateral pressure strength was measured by a KHKQ-100 type particle strength measuring instrument manufactured by Nanjing Ke-loop analysis Instrument Co.
More specifically, according to HG/T2782, pressure is applied to the cylindrical copper-silicon catalyst through a KHKQ-100 type particle strength tester, and when the cylindrical copper-silicon catalyst is broken, the KHKQ-100 type particle strength tester displays the maximum stress value which is the average lateral pressure strength.
The values of the average lateral pressure strength of the six cylindrical catalysts of examples 1 to 6 of the present invention are shown in Table 5, and the units are in Newton.
TABLE 5
Figure BDA0002813462700000151
The inventive examples also provide comparative example 1, comparative example 2 and comparative example 3.
In comparative example 1, 225.6 g of copper nitrate trihydrate was weighed and dissolved in 1.5 l of deionized water, ammonia was added to adjust the pH of the solution to 8-9, 225 g of silica microspheres were then poured into the solution uniformly and immersed for 8 hours with stirring at 80 ℃; and drying the obtained solid at 110 ℃ for 12h, and then roasting at 450 ℃ for 6h to obtain the spherical first comparative catalyst.
Specifically, the active component of the first comparative catalyst is copper oxide, and the carrier is silicon dioxide. The content of copper oxide was 34.5% and the content of silica was 65.5% by mass of the first comparative catalyst.
The spherical first comparative catalyst was tested using a KHKQ-100 type pellet Strength tester under the same test conditions as in examples 1-6 to have an average side pressure strength of 104.5 newtons, which was significantly lower than that of the cylindrical copper-silicon-based catalyst of the present application. It can be seen that, under the condition that the active component content and the carrier content are similar, although the content of the auxiliary agent in the copper-silicon catalyst of the application is not more than 5%, the good synergistic effect displayed among the active component, the composite carrier and the auxiliary agent is beneficial to improving the mechanical property of the catalyst.
In comparative example 2, 1200 ml of 1 mol/l aqueous copper nitrate solution, 2400 ml of 1 mol/l aqueous zinc nitrate solution and 100 ml of 3 mol/l aqueous aluminum nitrate solution were dissolved in deionized water, and then the solutions were quickly added to a 10-15% sodium carbonate solution at 80 ℃ with stirring, and then aged at 80 ℃ for 20min, and the resulting solid was washed, then 10 g of an auxiliary was added, and then filtered and dried, and the dried particles were calcined at 400 ℃ for 4 hours to obtain a second contrast catalyst in the form of particles. The second comparative catalyst is a copper catalyst commonly used in the industry at present and applied to preparing cyclohexanone by cyclohexanol dehydrogenation.
Specifically, the active component of the second comparative catalyst is copper oxide, and the carriers are zinc oxide and aluminum oxide. The copper oxide content is 43.5%, the zinc oxide content is 35.7%, and the aluminum oxide content is 20.8% by mass of the second comparative catalyst.
Specifically, the second comparative catalyst in the form of pellets was used to prepare a cylindrical second comparative catalyst having a diameter of 5 mm and a height of 5 mm by using the same forming agent and forming method as in example 1.
Specifically, the average side pressure strength of the cylindrical second comparative catalyst, which was measured using a KHKQ-100 type pellet Strength measuring apparatus under the same test conditions as in examples 1 to 6, was 123.7 newtons, which was significantly lower than that of the cylindrical copper-silicon-based catalyst of the present application.
Comparative example 3, an industrial catalyst provided by shanghai shengbang chemical ltd and having a product model of DHMAX-100 was selected as a third comparative catalyst.
Specifically, the active component of the third comparative catalyst is copper oxide, and the carrier is zinc oxide. The copper oxide content was 45.2% and the zinc oxide content was 54.8% by mass of the third comparative catalyst.
Specifically, the third comparative catalyst was a cylindrical catalyst having a diameter of 5 mm and a height of 3 mm.
Specifically, the third comparative catalyst, which was tested using a KHKQ-100 type pellet Strength tester under the same test conditions as in examples 1-6, exhibited an average side pressure strength of 153.1 newtons, which was significantly lower than that of the cylindrical copper-silicon-based catalyst of the present application.
The embodiment of the invention also provides an application of the copper-silicon catalyst in preparing cyclohexanone by dehydrogenation, which comprises the following steps: and placing the copper-silicon catalyst on a bed layer of a fixed bed reactor, carrying out catalyst reduction through a reducing gas to form a pretreated copper-silicon catalyst, and making a gaseous reactant flow through the pretreated copper-silicon catalyst to carry out an atmospheric dehydrogenation reaction.
Specifically, the reducing gas consists of hydrogen and inert atmosphere, the volume percentage of the hydrogen in the reducing gas is not less than 1%, the temperature of the catalyst reduction is 240-300 ℃, and the time duration is 2-24 hours.
Specifically, the temperature of the normal pressure dehydrogenation reaction is 190-230 ℃, the gaseous reactant is gaseous cyclohexanol, and the volume space velocity of the cyclohexanol is 0.5-3 hours-1。
The volumetric space velocity in the context of the present invention is defined as the volume of reactants per unit volume of catalyst per unit time.
Inventive example the cylindrical copper-silicon-based catalysts of examples 1 to 6, the spherical catalyst of comparative example 1, the cylindrical comparative catalyst of comparative example 2, and the cylindrical comparative catalyst of comparative example 3 were placed in the bed of the stainless reaction tube of the fixed bed reactor, respectively, to perform catalyst reduction and atmospheric dehydrogenation reactions.
Specifically, the loading volume of each catalyst was 50 ml, and the diameter of the stainless steel reaction tube was 5 cm.
Specifically, the filling volume refers to that the catalyst is filled into a container, and the catalyst is regularly vibrated under a certain condition, so that gaps among catalyst particles are compressed as much as possible, and finally, the volume that the gaps among the catalyst particles can not be reduced is achieved, so that the problem that materials are deflected due to the large gaps among the catalyst particles is solved.
Specifically, the catalyst is reduced by using a mixed gas of hydrogen and helium as a reducing gas, wherein the volume percentage of hydrogen in the reducing gas is 50%, the temperature for reducing the catalyst is 240 ℃, and the time is 4 hours, so that the copper-silicon catalyst is endowed with catalytic activity.
Specifically, after the catalyst is reduced, the temperature in the fixed bed reactor is adjusted to 230 ℃, the pressure is normal pressure, cyclohexanol is gasified by a gasification chamber to form a gaseous reactant, and then the gaseous reactant enters the fixed bed reactor and passes through the bed layer to contact with the catalyst to perform the normal pressure dehydrogenation reaction.
Condensing the product obtained by the normal pressure dehydrogenation reaction, performing gas-liquid separation, and then performing composition analysis on the obtained liquid phase product by using a gas chromatograph with the model of GC7900, so as to count the conversion rate W1 of cyclohexanol, the selectivity W2 of cyclohexanone, the content W3 of the byproduct cyclohexene, and the content W4 of the byproduct phenol, wherein the specific results are shown in Table 6. Table 6 also provides the reaction times t and the volume space velocity V1 of cyclohexanol for the different examples and comparative examples.
TABLE 6
Figure BDA0002813462700000181
Figure BDA0002813462700000191
From table 6, it can be seen that W1 is not less than 50%, W2 is not less than 99%, and is significantly higher than the three comparative examples, and it can be seen that good synergistic effect is achieved among the composite carrier, the active component and the auxiliary agent of the copper-silicon-based catalyst of the embodiment of the present invention.
The preparation process of the catalyst disclosed in CN102527385B is not beneficial to energy conservation and environmental protection, and the catalyst needs to be treated at the high temperature of 1000-1300 ℃ during preparation, thereby not only improving the production cost, but also increasing the energy consumption.
In addition, the cyclohexanol conversion in the method for preparing cyclohexanone by dehydrogenation of cyclohexanol disclosed in CN102527385B can be as high as 86.2%, but the reaction is carried out in a microreactor, and nitrogen is introduced into the reactor for reaction, so the actual reaction space velocity is very low and the reaction temperature is not labeled. As is common knowledge in the art, the process fluid channels of a microreactor are on the micron scale and its design and configuration are focused on the huge advantages in terms of mass transfer, heat transfer, thermostatting, etc., which are very costly in itself and mostly at the expense of yield, so that the microreactor is not suitable for large-scale process production of conventional chemicals.
The copper-silicon catalyst provided by the embodiment of the invention is applied to preparing cyclohexanone by cyclohexanol dehydrogenation, has good selectivity, and can effectively control the content of a byproduct cyclohexene to be not higher than 31ppm and the content of a byproduct phenol to be not higher than 62ppm, so that high-quality cyclohexanone is obtained.
Further, the present invention examined the changes of W1 and W2 by adjusting the temperatures of the atmospheric dehydrogenation reactions of each example and comparative example of table 6 to 240 degrees celsius and 260 degrees celsius, respectively, and maintaining the remaining process condition parameters constant. See table 7 for specific values of W1 and W2.
TABLE 7
Figure BDA0002813462700000192
Figure BDA0002813462700000201
Furthermore, the reaction time of the atmospheric dehydrogenation reaction is prolonged in examples 4 to 6 and the three comparative examples on the basis of the process parameters in Table 6, and the amounts of W1, W2, W3 after the continuous reaction time of 402 hours and W4 after the continuous reaction time of 836 hours are counted, and the specific values are shown in Table 8.
TABLE 8
Figure BDA0002813462700000202
The carbon deposition amounts W3 and W4 were obtained by thermal gravimetric analysis, specifically using a thermal gravimetric analyzer model STA 449F5 from the Navy (NETZSCH) company.
Specifically, a sample to be tested is heated from 50 ℃ to 800 ℃ at a heating rate of 10 ℃ per minute under an inert atmosphere nitrogen gas for thermogravimetric analysis to obtain ash, and the mass percentage of the ash in the sample to be tested is calculated to be W3 and W4 in Table 7. The operation process and the data processing process of the thermal loss analysis are well known to those skilled in the art, and are not described herein. Considering the test precision of the thermal weight loss analyzer, the numerical value of the carbon deposition amount below 0.05 percent cannot be read out.
As can be seen from tables 6 and 8, the copper-silicon based catalyst of the present invention was applied to the preparation of cyclohexanone by dehydrogenation of cyclohexanol, and even though the continuous reaction time was as high as 836 hours, the variations of W1 and W2 were not significant, and had good stability and catalytic activity as compared to the two comparative examples.
Further, the copper-silicon catalyst is applied to preparing cyclohexanone by cyclohexanol dehydrogenation, and the carbon deposition amount is controlled below 0.05 percent under the condition that the continuous reaction time is up to 402 hours; even if the continuous reaction time is further prolonged to 836 hours, the carbon deposition amount is still controlled to be not higher than 2.2 percent, and the carbon deposition resistance is good compared with the comparative ratio, thereby indicating that the copper-silicon catalyst has good catalytic activity.
Table 8 in combination with tables 6 and 7, it can be seen that as the reaction temperature of the atmospheric dehydrogenation reaction increases, W1 of all the examples and comparative examples significantly increases, the change in W2 is not significant, and it can be seen that the effect of temperature on conversion is greater. In view of this situation, especially in view of the importance of controlling the content of cyclohexene and phenol as by-products and improving the carbon deposition resistance of the catalyst, it is reasonable to control the temperature of the atmospheric dehydrogenation reaction to be not higher than 230 ℃.
Although the embodiments of the present invention have been described in detail hereinabove, it is apparent to those skilled in the art that various modifications and variations can be made to these embodiments. However, it is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention as described herein is capable of other embodiments and of being practiced or of being carried out in various ways.

Claims (13)

1. A copper-silicon catalyst is applied to the reaction of preparing cyclohexanone by cyclohexanol dehydrogenation, and is characterized in that:
the copper-silicon catalyst comprises an active component, a composite carrier and an auxiliary agent;
the copper-silicon catalyst comprises, by mass, 32-45% of the active ingredient, 45-70% of the composite carrier and 1-5% of the auxiliary agent;
the active component is copper oxide, the composite carrier is composed of silicon oxide and zirconium oxide, and the auxiliary agent is any one of alkali metal oxide and alkaline earth metal oxide.
2. The copper-silicon-based catalyst according to claim 1, wherein the copper oxide is cuprous oxide, the alkali metal oxide is any one of sodium oxide and potassium oxide, and the alkaline earth metal oxide is any one of calcium oxide, magnesium oxide, strontium oxide, and barium oxide.
3. The Cu-Si-based catalyst as claimed in claim 1, wherein the Cu-Si-based catalyst has a specific surface area of 205-285 m/g, a pore volume of 0.25-0.65 m/g, and an average pore diameter of 4.0-10.5 nm.
4. The copper-silicon catalyst according to claim 1, further comprising a forming agent, wherein the forming agent is contained in the copper-silicon catalyst in such a manner that the copper-silicon catalyst is columnar, the average lateral pressure strength of the columnar copper-silicon catalyst is not less than 200 newtons, and the forming agent is contained in an amount of not more than 6% by mass of the copper-silicon catalyst.
5. A method for preparing the copper-silicon-based catalyst according to any one of claims 1 to 4, comprising:
s0: providing a primary carrier, a cuprammonium solution and a mixed solution, wherein the primary carrier contains a silicon precursor and a zirconium precursor loaded on the surface of the silicon precursor, and the mixed solution contains a precursor of the auxiliary agent;
s1: sequentially carrying out first dipping treatment, ammonia evaporation treatment and washing and drying treatment on the original carrier through the copper ammonia solution, so that copper ions in the copper ammonia solution are loaded on the surface of the original carrier to obtain an intermediate precursor;
s2: carrying out second dipping treatment on the intermediate precursor through the mixed solution, and then sequentially carrying out drying treatment and roasting treatment on the obtained wet carrier;
in the copper ammonia solution, the molar ratio of ammonia to copper is 2.5-3.5, the mass ratio of the original carrier to copper in the copper ammonia solution is 1.5-2.0, and the mass ratio of the intermediate precursor to the precursor of the auxiliary agent is 15-60.
6. The method as claimed in claim 5, wherein the copper ammonia solution has a pH of 10-11, the valence of copper in the copper ammonia solution is positive, the ammonia evaporation process is performed at a temperature of 70-90 ℃ and a pressure of 0.06-0.1 MPa in step S1, the pH of the steam is detected during the ammonia evaporation process, and the ammonia evaporation process is stopped when the pH of the steam is 7.0-7.5.
7. The method according to claim 6, wherein a copper precursor, an ammonium precipitant, and ammonia water are used to prepare a raw copper ammonia solution, and the raw copper ammonia solution is subjected to a reduction treatment with hydrogen gas for 4 to 18 hours under an inert atmosphere to obtain the copper ammonia solution.
8. The method according to claim 7, wherein the copper precursor comprises at least one of copper metal, copper oxide, copper nitrate and copper acetate, and the ammonium precipitant is an alkaline substance containing ammonia or a salt substance containing ammonium ions.
9. The preparation method according to claim 5, wherein after the completion of step S2, a forming agent is mixed with the catalyst powder obtained by the calcination treatment and then subjected to a tabletting treatment to obtain the columnar copper-silicon-based catalyst, and the forming agent accounts for not more than 6% by mass of the columnar copper-silicon-based catalyst.
10. The preparation method according to claim 5, wherein the silicon precursor is silicon powder, the particle size of the silicon powder is 5-30 μm, the specific surface area is 100-400 square meters per gram, the zirconium precursor is at least one of zirconium nitrate, zirconium acetate and zirconium chloride, the zirconium precursor is loaded on the surface of the silicon precursor through a precipitant, and the precipitant is an alkaline substance containing ammonia or a salt substance containing ammonium ions.
11. The method according to claim 5, wherein the precursor of the auxiliary agent is any one of an alkali metal water-soluble salt and an alkaline earth metal water-soluble salt, the alkali metal element in the alkali metal water-soluble salt is any one of sodium and potassium, and the alkaline earth metal element in the alkaline earth metal water-soluble salt is any one of calcium, magnesium, strontium and barium.
12. Use of a copper silicon based catalyst according to any of claims 1 to 4 for the dehydrogenation of cyclohexanone, comprising:
placing the copper-silicon catalyst in a bed layer of a fixed bed reactor, carrying out catalyst reduction through reducing gas to form a pretreated copper-silicon catalyst, and enabling gaseous reactant to flow through the pretreated copper-silicon catalyst to carry out normal-pressure dehydrogenation reaction;
the temperature of the normal pressure dehydrogenation reaction is 190 ℃ and 230 ℃, soThe gaseous reactant is gaseous cyclohexanol, and the volume space velocity of the cyclohexanol is 0.6-3 hours-1。
13. The method as claimed in claim 12, wherein the reducing gas is composed of hydrogen and an inert atmosphere, the hydrogen in the reducing gas accounts for not less than 1% of the volume of the reducing gas, and the catalyst is reduced at a temperature of 240 ℃ and 300 ℃ for a period of 2-24 hours.
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WO1998010864A1 (en) * 1996-09-11 1998-03-19 Basf Aktiengesellschaft Catalyst for preparing cyclohexanone by dehydrogenation of cyclohexanol and process for the preparation thereof
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