CN112657499A - Catalyst for oxidizing cyclohexane by carbon dioxide and preparation method and application thereof - Google Patents
Catalyst for oxidizing cyclohexane by carbon dioxide and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of carbon dioxide chemical utilization, and relates to a catalyst for oxidizing cyclohexane by carbon dioxide, and a preparation method and application thereof2The carbon-chemical is obtained by catalytic conversion. The catalyst active component is at least one of Cu, Ni, Pt, Pd, Ru, Au, Ag and Rh, the cocatalyst component is at least one of alkali metal, alkaline earth metal and rare earth element oxide, and the carrier component is SiO2、Al2O3、ZrO2At least one of active carbon and molecular sieve. The technology of the invention can simultaneously solve the problem of utilization of the cyclohexane byproduct in the process of preparing cyclohexanone by using the cyclohexene hydration method and the problem of emission reduction of carbon dioxide, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide chemical utilization, and particularly relates to a catalyst for oxidizing cyclohexane by carbon dioxide, and a preparation method and application thereof.
Background
Carbon dioxide is a main greenhouse gas on the earth, the concentration of the carbon dioxide increases year by year and has a plurality of adverse effects on the earth biosphere, and the emission reduction of the carbon dioxide becomes a hot spot of global attention. The use of carbon dioxide as a raw material for the synthesis of chemicals is the most effective route for carbon dioxide remediation. The preparation of cyclohexanol from benzene, the dehydrogenation of cyclohexanol to cyclohexanone, the preparation of caprolactam from cyclohexanone and the preparation of downstream products nylon-6 or nylon-6 polyamide chips are the current mature technical routes. There are three different technical routes from benzene to cyclohexanol: benzene hydrogenation-cyclohexane oxidation method, benzene partial hydrogenation-cyclohexene hydration method, and benzene partial hydrogenation-cyclohexene esterification hydrogenation method, wherein cyclohexane is the main byproduct of benzene partial hydrogenation in the latter two methods. The cyclohexane oxidation method for preparing cyclohexanol has the problems of more side reactions, poorer process safety and the like, partial hydrogenation of benzene, cyclohexene and cyclohexanol is a future technical development trend, but the application problem of the byproduct cyclohexane is solved. If cyclohexane can be converted into cyclohexene or benzene again, and the product can enter a reaction system for synthesizing cyclohexanol again, the economy of preparing cyclohexanol by using a cyclohexene method is greatly improved. Cyclohexene or benzene is obtained by a cyclohexane dehydrogenation route in the prior art. For example, chinese patent CN104785256B discloses a preparation method and application of a catalyst for cyclohexene dehydrogenation, wherein the catalyst comprises a carrier and a main catalyst, the carrier is Mg-Al composite oxide, the cocatalyst is selected from at least one of tin, indium and gallium, the main catalyst is selected from at least one of platinum, palladium, osmium, iridium, ruthenium and rhodium, the preparation method utilizes an impregnation method of microwave-assisted calcination, the cyclohexane conversion rate can reach 3.8%, and the cyclohexene selectivity can reach 84.1%. Therefore, the efficiency of the reaction still has room for improvement.
Disclosure of Invention
The invention aims to provide a method for efficiently converting cyclohexane into benzene or cyclohexene and converting greenhouse gas carbon dioxide into an important carbon chemical raw material or a carbon product.
The main characteristic of the invention is to creatively use CO through the design of catalyst components and the advanced catalyst preparation method2As the oxidant of the cyclohexane, the efficient dehydrogenation and CO of the cyclohexane are realized2And (4) chemical utilization.
The purpose of the invention is realized by the following technical scheme:
the invention provides a carbon oxide-oxidized cyclohexane catalyst, wherein the active component of the catalyst is one of Cu, Ni, Pt, Pd, Ru, Au, Ag and Rh, the promoter component is at least one of alkali metal, alkaline earth metal and rare earth element oxide, and the carrier component is SiO2、Al2O3、ZrO2One of active carbon and molecular sieve.
Preferably, the alkali metal is Na2O and K2O; the alkaline earth metal is MgO, CaO, SrO and BaO; the rare earth element oxide is La2O3And CeO2。
Preferably, the mass ratio of the active component of the catalyst, the cocatalyst and the carrier is 5-30: 2-10: 20-60.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
a. treating a carrier under a water vapor condition, and impregnating the carrier with a promoter component soluble salt solution to obtain a precursor 1;
b. carrying out heat treatment on the impregnated precursor 1 in air, and then carrying out treatment in a reducing atmosphere to obtain a precursor 2;
c. and (3) impregnating the precursor 2 with a catalyst active component soluble salt solution, carrying out heat treatment on the impregnated precursor 2 in nitrogen, and then treating in a reducing atmosphere to obtain the catalyst for preparing cyclohexene by oxidizing cyclohexane with carbon dioxide.
Preferably, the steam treatment condition in the step a is saturated steam, the temperature is 80-100 ℃, and the treatment time is 4-10 h.
Preferably, the impregnation in the steps a and c is excessive impregnation, the impregnation temperature is 25-90 ℃, and the impregnation time is 2-10 h.
Preferably, the air treatment temperature in the step b is 200-600 ℃, and the treatment time is 4-10 h.
Preferably, the reducing atmosphere in the steps b and c is hydrogen-nitrogen mixed gas containing 5-30% of hydrogen by volume concentration, the treatment temperature is 250-550 ℃, and the treatment time is 2-10 hours.
The invention also provides an application of the catalyst, the catalyst is used for a reaction of oxidizing cyclohexane by carbon dioxide, the catalyst is shaped into a sphere with the diameter of phi 3-5 mm, the molar ratio of carbon dioxide to cyclohexane in the raw materials is 0.1-3.5, and the hourly space velocity of cyclohexane liquid is 0.5-10 h-1The reaction temperature is 250-650 ℃, and the pressure is 1-10 MPa.
The catalyst is applied to the reaction of oxidizing cyclohexane with carbon dioxide, and the product comprises at least one of benzene and cyclohexene and at least one of methane, methanol, formic acid and carbon monoxide besides water.
Advantageous effects
The catalyst prepared by the method is applied to the reaction of oxidizing cyclohexane by carbon dioxide, the cyclohexane conversion rate is high, the hydrogen utilization rate is high, and CO is generated2The conversion rate is high.
Detailed Description
The following examples are intended to further illustrate the invention and are not intended to limit the invention.
Example 1
The active component of the catalyst is copper, the cocatalyst is zinc oxide and magnesium oxide, and the carrier is aluminum oxide. Wherein, the ratio of copper: zinc oxide: magnesium oxide: the mass ratio of the alumina is 5:2:8: 60.
Treating the alumina in saturated vapor at 80 ℃ for 10h to obtain alumina-1; weighing zinc nitrate and magnesium nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 90 ℃, soaking aluminum oxide-1 in the saturated nitrate solution for 2 hours to obtain a precursor 1, treating the precursor for 2 hours at 600 ℃ in the air, and reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 30% of hydrogen at 550 ℃ to obtain a precursor 2; weighing copper nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 90 ℃, soaking the precursor 2 in the saturated nitrate solution for 2 hours, then treating the precursor for 2 hours in nitrogen at 300 ℃, and then reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 20% of hydrogen at 550 ℃ to obtain the catalyst cat 1.
The cat1 is shaped into a spherical shape with the diameter of 3-5 mm and is used for the reaction of oxidizing cyclohexane by carbon dioxide, the molar ratio of carbon dioxide/cyclohexane in the raw materials is 3.5, and the hourly space velocity of cyclohexane liquid is 10h-1The reaction temperature is 250 ℃, the pressure is 5MPa, the conversion rate of cyclohexane is 98.1 percent, and CO is2The conversion was 25.7%, the benzene selectivity was 99.7%, and the methanol selectivity was 99.2%.
Example 2
The catalyst comprises nickel as an active component, potassium oxide and magnesium oxide as a cocatalyst, and zirconium oxide as a carrier. Wherein, the ratio of nickel: potassium oxide: magnesium oxide: the mass ratio of zirconia is 30:1:1: 20.
Treating zirconia in saturated steam at 100 ℃ for 4h to obtain zirconia-1; weighing potassium nitrate and magnesium nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 50 ℃, soaking zirconium oxide-1 in the saturated nitrate solution for 4 hours to obtain a precursor 1, treating the precursor for 4 hours at 200 ℃ in the air, and reducing the precursor for 10 hours in hydrogen-nitrogen mixed gas containing 5% of hydrogen at 250 ℃ to obtain a precursor 2; weighing nickel nitrate according to the composition proportion of the catalyst, preparing saturated nitrate solution by using deionized water at 50 ℃, soaking the precursor 2 in the saturated nitrate solution for 2 hours, then treating the precursor for 2 hours in nitrogen at 300 ℃, and then reducing the precursor for 4 hours in hydrogen-nitrogen mixed gas containing 10% of hydrogen at 250 ℃ to obtain the catalyst cat 2.
The cat2 is shaped into a spherical shape with the diameter of 3-5 mm and is used for the reaction of oxidizing cyclohexane by carbon dioxide, the molar ratio of carbon dioxide/cyclohexane in the raw materials is 0.1, and the hourly space velocity of cyclohexane liquid is 5h-1The reaction temperature is 600 ℃, the pressure is 3MPa, the cyclohexane conversion rate is 99.1 percent, and CO is2The conversion was 80.9%, the cyclohexene selectivity was 97.9%, and the methane selectivity was 99.8%.
Example 3
The active component of the catalyst is platinum, the cocatalyst is sodium oxide and calcium oxide, and the carrier is silicon oxide. Wherein, the ratio of platinum: sodium oxide: calcium oxide: the silicon oxide (mass ratio) was 10:5:3: 30.
Treating the silicon oxide in saturated steam at 100 ℃ for 4h to obtain silicon oxide-1; weighing sodium nitrate and calcium nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 60 ℃, soaking silicon oxide-1 in the saturated nitrate solution for 4 hours to obtain a precursor 1, treating the precursor for 3 hours at 400 ℃ in the air, and reducing the precursor for 10 hours in hydrogen-nitrogen mixed gas containing 5% of hydrogen at 300 ℃ to obtain a precursor 2; according to the composition proportion of the catalyst, 5 percent chloroplatinic acid solution is measured, the precursor 2 is soaked in the chloroplatinic acid solution for 2 hours at 50 ℃, then is treated in nitrogen at 300 ℃ for 2 hours, and is reduced in hydrogen-nitrogen mixed gas containing 10 percent of hydrogen at 300 ℃ for 4 hours to obtain the catalyst cat 3.
The cat3 is shaped into a spherical shape with the diameter of 3-5 mm and is used for the reaction of oxidizing cyclohexane by carbon dioxide, the molar ratio of carbon dioxide/cyclohexane in the raw materials is 1.2, and the hourly space velocity of cyclohexane liquid is 5h-1The reaction temperature is 300 ℃, the pressure is 3MPa, the cyclohexane conversion rate is 99.5 percent, and CO is2Conversion rate90 percent, the selectivity of cyclohexene is 98.9 percent, and the selectivity of carbon monoxide is 99.8 percent.
Example 4
The active component of the catalyst is copper, the cocatalyst is zinc oxide and strontium oxide, and the carrier is HZSM-5 molecular sieve. Wherein, the ratio of copper: zinc oxide: strontium oxide: the weight ratio of the HZSM-5 molecular sieve is 30:2:2: 30.
Treating the molecular sieve in saturated steam at 70 ℃ for 10h to obtain molecular sieve-1; weighing zinc nitrate and strontium nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 60 ℃, soaking a molecular sieve-1 in the saturated nitrate solution for 3 hours to obtain a precursor 1, treating the precursor for 2 hours at 500 ℃ in air, and reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 30% of hydrogen at 450 ℃ to obtain a precursor 2; weighing copper nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 90 ℃, soaking the precursor 2 in the saturated nitrate solution for 2 hours, then treating the precursor for 2 hours in nitrogen at 300 ℃, and then reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 50% of hydrogen at 350 ℃ to obtain the catalyst cat 4.
The cat4 is shaped into a spherical shape with the diameter of 3-5 mm and is used for the reaction of oxidizing cyclohexane by carbon dioxide, the molar ratio of carbon dioxide/cyclohexane in the raw materials is 3.5, and the hourly space velocity of cyclohexane liquid is 10h-1The reaction temperature is 250 ℃, the pressure is 5MPa, the conversion rate of cyclohexane is 98.1 percent, and CO is2The conversion was 26.9%, the cyclohexene selectivity was 96.7%, and the methanol selectivity was 99.8%.
Example 5
The active components of the catalyst are copper and gold, the promoters are zinc oxide and cerium oxide, and the carrier is aluminum oxide. Wherein, the ratio of copper: gold: zinc oxide: cerium oxide: the mass ratio of the aluminum oxide is 20:10:2:2: 30.
Treating the alumina in saturated vapor at 40 ℃ for 10h to obtain alumina-1; weighing zinc nitrate and cerium nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 70 ℃, soaking aluminum oxide-1 in the saturated nitrate solution for 3 hours to obtain a precursor 1, treating the precursor for 2 hours at 500 ℃ in the air, and reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 30% of hydrogen at 450 ℃ to obtain a precursor 2; weighing copper nitrate according to the composition proportion of the catalyst, dissolving the copper nitrate in 10 percent chloroauric acid solution, soaking the precursor 2 in the solution for 5 hours at 90 ℃, then treating the solution for 2 hours in nitrogen at 300 ℃, and then reducing the solution for 2 hours in hydrogen-nitrogen mixed gas with 50 percent hydrogen at 450 ℃ to obtain the catalyst cat 5.
The cat5 is shaped into a spherical shape with the diameter of 3-5 mm and is used for the reaction of oxidizing cyclohexane by carbon dioxide, the molar ratio of carbon dioxide/cyclohexane in the raw materials is 1, and the hourly space velocity of cyclohexane liquid is 1h-1The reaction temperature is 300 ℃, the pressure is 10MPa, the conversion rate of cyclohexane is 98.1 percent, and CO is2The conversion was 89.7%, the cyclohexene selectivity was 96.7%, and the formic acid selectivity was 92.8%.
Example 6
The catalyst comprises active components of nickel and gold, a promoter of zinc oxide and cerium oxide, and a carrier of aluminum oxide. Wherein, the ratio of nickel: gold: zinc oxide: cerium oxide: the mass ratio of the aluminum oxide is 20:10:2:2: 30.
Treating the alumina in saturated vapor at 40 ℃ for 10h to obtain alumina-1; weighing zinc nitrate and cerium nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 70 ℃, soaking aluminum oxide-1 in the saturated nitrate solution for 3 hours to obtain a precursor 1, treating the precursor for 2 hours at 500 ℃ in the air, and reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 30% of hydrogen at 450 ℃ to obtain a precursor 2; weighing nickel nitrate according to the composition proportion of the catalyst, dissolving the nickel nitrate in 10% chloroauric acid solution, soaking the precursor 2 in the solution for 5 hours at 90 ℃, then treating the solution for 2 hours in nitrogen at 300 ℃, and then reducing the solution for 2 hours in hydrogen-nitrogen mixed gas containing 50% hydrogen at 450 ℃ to obtain the catalyst cat 6.
The cat6 is shaped into a spherical shape with the diameter of 3-5 mm and is used for the reaction of oxidizing cyclohexane by carbon dioxide, the molar ratio of carbon dioxide/cyclohexane in the raw materials is 1, and the hourly space velocity of cyclohexane liquid is 1h-1The reaction temperature is 300 ℃, the pressure is 10MPa, the conversion rate of cyclohexane is 99.1 percent, and CO is2The conversion was 91.7%, the cyclohexene selectivity was 98.7%, and the formic acid selectivity was 96.8%.
Example 7
The active components of the catalyst are platinum and gold, the catalyst promoter is zinc oxide and cerium oxide, and the carrier is aluminum oxide. Wherein, the ratio of platinum: gold: zinc oxide: cerium oxide: the mass ratio of the aluminum oxide is 1:29:2:2: 30.
Treating the alumina in saturated vapor at 40 ℃ for 10h to obtain alumina-1; weighing zinc nitrate and cerium nitrate according to the composition proportion of the catalyst, preparing a saturated nitrate solution by using deionized water at 70 ℃, soaking aluminum oxide-1 in the saturated nitrate solution for 3 hours to obtain a precursor 1, treating the precursor for 2 hours at 500 ℃ in the air, and reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 30% of hydrogen at 450 ℃ to obtain a precursor 2; weighing a mixed solution of aluminum platinic acid and chloroauric acid according to the composition proportion of the catalyst, wherein the total concentration is 10%, soaking the precursor 2 in the mixed solution for 3 hours at 90 ℃, then treating the precursor for 2 hours in nitrogen at 300 ℃, and then reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 50% of hydrogen at 550 ℃ to obtain the catalyst cat 7.
The cat7 is shaped into a spherical shape with the diameter of 3-5 mm and is used for the reaction of oxidizing cyclohexane by carbon dioxide, the molar ratio of carbon dioxide/cyclohexane in the raw materials is 1, and the hourly space velocity of cyclohexane liquid is 1h-1The reaction temperature is 300 ℃, the pressure is 10MPa, the cyclohexane conversion rate is 99.8 percent, and CO is2The conversion was 95.7%, the cyclohexene selectivity was 99.7%, and the formic acid selectivity was 99.8%.
Example 8
The active components of the catalyst are ruthenium and silver, the catalyst promoter is barium oxide and lanthanum oxide, and the carrier is aluminum oxide. Wherein, ruthenium: silver: barium oxide: lanthanum oxide: the mass ratio of the aluminum oxide is 20:10:2:2: 30.
Treating the alumina in saturated vapor at 40 ℃ for 10h to obtain alumina-1; weighing barium nitrate and lanthanum nitrate according to the composition proportion of a catalyst, preparing a saturated nitrate solution by using deionized water at 70 ℃, soaking aluminum oxide-1 in the saturated nitrate solution for 3 hours to obtain a precursor 1, treating the precursor for 2 hours at 500 ℃ in air, and reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 30% of hydrogen at 450 ℃ to obtain a precursor 2; weighing silver nitrate according to the composition proportion of the catalyst, dissolving the silver nitrate in a ruthenium nitrate solution, soaking the precursor 2 in the ruthenium nitrate solution for 5 hours at 90 ℃, then treating the precursor for 2 hours in nitrogen at 300 ℃, and then reducing the precursor for 2 hours in hydrogen-nitrogen mixed gas containing 50% of hydrogen at 450 ℃ to obtain the catalyst cat 8.
The cat8 is shaped into a round ball with the diameter of 3-5 mm and is used for the reaction of oxidizing cyclohexane by carbon dioxide, and the carbon dioxide is dissolved in the raw materialThe cyclohexane molar ratio is 1, the cyclohexane liquid hourly space velocity is 1h-1The reaction temperature is 300 ℃, the pressure is 10MPa, the conversion rate of cyclohexane is 99.1 percent, and CO is2The conversion was 89.7%, the cyclohexene selectivity was 96.4%, and the formic acid selectivity was 94.8%.
Claims (10)
1. The catalyst for oxidizing cyclohexane by carbon dioxide is characterized in that the active component of the catalyst is at least one of Cu, Ni, Pt, Pd, Ru, Au, Ag and Rh, the promoter component is at least one of alkali metal, alkaline earth metal and rare earth element oxide, and the carrier component is SiO2、Al2O3、ZrO2At least one of active carbon and molecular sieve.
2. The catalyst of claim 1, wherein the alkali metal is Na2O and K2O; the alkaline earth metal is MgO, CaO, SrO and BaO; the rare earth element oxide is La2O3And CeO2。
3. The catalyst according to claim 1, wherein the mass ratio of the catalyst active component, the cocatalyst and the carrier is 5-30: 2-10: 20-60.
4. The method for preparing the catalyst according to claim 1,
a. treating a carrier under a water vapor condition, and impregnating the carrier with a promoter component soluble salt solution to obtain a precursor 1;
b. carrying out heat treatment on the impregnated precursor 1 in air, and then carrying out treatment in a reducing atmosphere to obtain a precursor 2;
c. and (2) impregnating the precursor 2 with a catalyst active component soluble salt solution, carrying out heat treatment on the impregnated precursor 2 in nitrogen, and then carrying out treatment in a reducing atmosphere to obtain the catalyst.
5. The preparation method according to claim 4, wherein the steam treatment in step a is carried out under saturated steam at 80-100 ℃ for 4-10 h.
6. The method of claim 4, wherein the impregnation in steps a and c is an excess impregnation, the impregnation temperature is 25 to 90 ℃, and the impregnation time is 2 to 10 hours.
7. The preparation method according to claim 4, wherein the air treatment temperature in the step b is 200 to 600 ℃ and the treatment time is 4 to 10 hours.
8. The preparation method of claim 4, wherein the reducing atmosphere in steps b and c is a hydrogen-nitrogen mixed gas containing 5-30% by volume of hydrogen, the treatment temperature is 250-550 ℃, and the treatment time is 2-10 h.
9. The application of the catalyst of claim 1, wherein the catalyst is used for the reaction of oxidizing cyclohexane by carbon dioxide, the catalyst is shaped into a sphere with a diameter of 3-5 mm, the molar ratio of carbon dioxide/cyclohexane in the raw material is 0.1-3.5, and the hourly space velocity of cyclohexane liquid is 0.5-10 h-1The reaction temperature is 250-650 ℃, and the pressure is 1-10 MPa.
10. The use of claim 9, wherein the catalyst is used in a reaction for oxidizing cyclohexane with carbon dioxide, and the product comprises, in addition to water, at least one of benzene and cyclohexene, and at least one of methane, methanol, formic acid, and carbon monoxide.
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| CN113617354A (en) * | 2021-07-08 | 2021-11-09 | 南京红太阳生物化学有限责任公司 | 3-methylpiperidine dehydrogenation catalyst, and preparation method and application thereof |
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