Multifunctional copper-based catalyst and method for its preparation

Abstract

The application provides a multifunctional copper-based catalyst and a preparation method thereof, and the copper-based catalyst comprises catalyst particles, the catalyst particles comprise an aluminum carrier and an active component supported on the aluminum carrier, and the active component comprises copper and zinc; in the catalyst particles, the content of the aluminum carrier is 1-40 wt%, the content of copper is 10-70 wt%, and the content of zinc is 5-60 wt% in terms of mass fraction of oxides. The application changes the content and distribution of the active component in the catalyst through multiple precipitation and impregnation steps, so that the purpose of preparing multiple functional catalysts by one preparation method is achieved. Compared with the catalyst prepared by a traditional method, the catalyst prepared by the method has the advantages of high activity, strong adaptability, good thermal stability and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalysts, and particularly relates to a multifunctional copper-based catalyst and a preparation method thereof. BACKGROUND

[0002] The influence of the preparation method on the catalyst is very obvious. The physical and chemical properties of the catalyst prepared from the same raw material are different due to different preparation methods, and finally affect the reaction activity and stability of the catalyst. At present, the preparation methods of the catalyst mainly include coprecipitation method, impregnation method, impregnation precipitation method, sol-gel method, microemulsion method, acid-alkali alternating method, and azeotropic distillation method. Among them, the coprecipitation method has the widest application range. The Cu-based catalyst prepared by the coprecipitation method can uniformly disperse CuO in the ZnO component. With the increase of the Cu content, the number of the best active units in the catalyst increases, the synergistic promotion effect between the Cu / Zn components increases, and the catalytic activity is improved. After decades of research, it is found that the catalyst prepared by the coprecipitation method has the best activity and stability.

[0003] (1) Coprecipitation method

[0004] The coprecipitation method is to first coprecipitate the metal solution with a precipitant, and then prepare the catalyst by aging, washing, suction filtration, drying, calcination and molding. The coprecipitation method can be divided into forward addition method, reverse addition method and parallel flow method. Generally, the activity of the catalyst prepared by the three methods is in the order of parallel flow method > reverse addition method > forward addition method.

[0005] Guo Xianji et al. prepared three Cu / ZnO / Al2O3 catalysts with the same composition by using three different precipitation methods (forward addition, reverse addition and parallel flow). The activity order of the catalysts is: parallel flow sample > reverse addition sample > forward addition sample; and the reduction temperature order from low to high is: reverse addition sample < parallel flow sample < forward addition sample. Through DTA analysis of the catalyst precursor, it is confirmed that the precipitation behaviors of Cu 2+ and Zn 2+ in the three precipitation processes are different, that is, in the parallel flow and reverse addition precipitation processes, Cu 2+ and Zn 2+ are uniformly precipitated at the same time, and the copper and zinc components form a uniformly dispersed coprecipitate material, and the obtained catalyst sample (oxidation state) has strong interaction between CuO and ZnO components and is easy to reduce. In the forward addition precipitation process, Cu 2+ and Zn 2+Stepwise precipitation occurred. The interaction between CuO and ZnO components in the obtained catalyst sample (oxidized state) was weak, and the reduction temperature was high. Although the reverse addition method could more evenly disperse the copper and zinc components and the obtained catalyst (oxidized state) had smaller crystal grains than the co-current method, the catalytic activity of the reverse addition method sample was not higher than that of the co-current method sample due to the influence of the reduction process.

[0006] (2) Impregnation method

[0007] The impregnation method is to load copper salt onto the carrier by impregnation, and then to prepare the catalyst through drying, calcination and molding. Liu Yuan et al. prepared CuO-ZrO2 catalyst for methanol synthesis by the impregnation method, studied the CO + H2 methanol synthesis process, and showed good activity and selectivity. They believed that the activity of the catalyst mainly depended on the interaction between Cu and Zr. Zhang Zhiyong et al. prepared a series of Cu-ZnO-Al2O3 catalysts by the impregnation method, and investigated the influence of catalyst calcination temperature and composition on the performance of the methanol steam conversion reaction for hydrogen production. Through characterization, it was found that when the calcination temperature was 400°C and the Cu / Zn / Al ratio was 1:1:3.2, the catalyst had the best performance. Song Weilin et al. prepared Cu / Mn / Mg / K catalyst and traditional Cu / Zn / Al methanol cracking catalyst using Ti-modified AL2O3, activated carbon, silica gel and molecular sieve as carriers, respectively. Through characterization, it was found that the performance of the Cu / Mn / Mg / K catalyst for methanol cracking was better than that of the Cu / Zn / Al, and the catalyst prepared using Al2O3 as the carrier had the best performance.

[0008] (3) Impregnation precipitation method

[0009] The impregnation precipitation method is to add the carrier to the copper salt solution, form a suspension, and then precipitate copper onto the carrier under the action of a precipitant. Then the precipitate is aged, washed, filtered, dried, calcined and reduced to prepare the catalyst.

[0010] (4) Sol-gel method

[0011] The sol-gel method involves the hydrolysis or alcoholysis of copper and zirconium salts under the action of a precipitant to obtain a hydrogel, which is then converted into a dry gel or aerogel under certain conditions. Zhu Yiqing et al. prepared an ultrafine CuO-ZnO / SiO2-ZrO2 catalyst for the synthesis of methanol from CO2 and H2 using the gel-sol method. The CuO crystallites were less than 16 nm in size. This catalyst exhibited a large specific surface area, high dispersion of active components, and high selectivity and catalytic activity. Cong Yu et al. prepared an ultrafine Cu-ZnO-ZrO2 catalyst with an average particle size of 26 nm using the gel-sol method, which showed good activity in the synthesis of methanol from CO2 and H2. Although catalysts prepared by the sol-gel method exhibit certain catalytic activity, the preparation process is very cumbersome, the preparation conditions are harsh, metal alkoxides are used as raw materials, which are expensive, toxic, flammable, and difficult to store.

[0012] (5) Microemulsion method

[0013] The microemulsion method involves the formation of an emulsion from two immiscible solvents under the action of a surfactant, followed by the precipitation of a solid material from the emulsion. The Cu / ZrO2 catalyst prepared by the microemulsion method is obtained by adding a measured amount of surfactant to a mixture of n-hexane and copper nitrate under vigorous stirring to form a microemulsion. Then, a zirconium salt-containing n-butanol solution is added dropwise to the microemulsion. After vigorous stirring for a period of time, the mixture is precipitated, washed, filtered, dried, and calcined.

[0014] (6) Acid-base alternation method

[0015] The acid-base alternation method involves adding Cu(NO3)2, Zn(NO3)2, Al(NO3)3, and Zr(NO3)4 solutions to a flask under stirring. The pH of the mixed salt solution is adjusted to alkaline using Na2CO3 solution, and then the pH of the mother liquor is adjusted to acidic using the mixed salt solution. The mother liquor is alternated between neutral, alkaline, acidic, and neutral for one cycle. After precipitation, the precipitate mixture is aged, washed, filtered, dried, calcined, and shaped to obtain the methanol catalyst.

[0016] Wu Zaiguo et al. prepared a methanol synthesis catalyst using an acid-base alternating precipitation method. Their research found that the Cu / Zn component in the catalyst existed as an amorphous CuO-ZnO solid solution. Due to the small size, uniform particle size distribution, and low crystallinity of CuO and ZnO crystals, the specific surface area of ​​the catalyst was increased, thereby enhancing the dispersion of the active components. Cen Yaqing et al. studied the effects of mother liquor pH and the number of alternations on catalyst performance. Their results showed that the catalyst exhibited the best activity when the pH alternation range was 5.0–9.5 and the number of alternations was 3. Compared with other preparation methods, the catalyst prepared by this method possessed very high reactivity and high-temperature resistance; after heat treatment, the catalyst activity retention rate remained as high as 88%, which is 8–20% higher than other general catalysts.

[0017] (7) Azeotropic distillation

[0018] The azeotropic distillation method involves preparing a 0.11 mol / L solution of Cu(NO3)2, Zn(NO3)2, and Zr(NO3)4 under stirred conditions. 9% ammonia solution is slowly added dropwise until the pH reaches 7.0. After appropriate dehydration of the precipitate, a n-butanol solution is added. Azeotropic distillation is then carried out under continuous stirring and heating. When the vapor temperature reaches the boiling point of n-butanol, the mixture is refluxed for 30 minutes, then dried at low temperature to remove the organic solvent, and finally calcined at 500℃ for 4 hours to obtain the methanol synthesis catalyst.

[0019] Cong Yu et al. prepared an ultrafine Cu-ZnO-ZrO2 methanol synthesis catalyst using azeotropic distillation. The catalyst had an average particle size of 14 nm and a relatively uniform particle distribution, but the dispersion of the active components was poor. When applied to the synthesis of methanol from CO2 and H2, the reaction temperature at which the methanol space-time yield was maximized was about 25 °C lower than that of industrial catalysts. The space-time yield and selectivity of methanol were higher than those of the coprecipitation method and the sol-gel method.

[0020] (8) Parallel slurry mixing method

[0021] Guo Xianji et al. prepared a series of Cu / ZnO / Al2O3 catalysts with different copper-zinc-aluminum ratios using a co-current slurry mixing method. The experimental results showed that the catalysts prepared by this method still had high activity when reacting at higher temperatures (520K~560K).

[0022] Other methods include two-step loading, oxalate colloidal coprecipitation, and supercritical ethanol fluid drying. Summary of the Invention

[0023] To address the aforementioned problems in the prior art, this invention proposes a multifunctional copper-based catalyst and its preparation method.

[0024] In a first aspect, the present invention proposes a multifunctional copper-based catalyst, the copper-based catalyst comprising catalyst particles, the catalyst particles comprising an aluminum support and an active component supported on the aluminum support, wherein the active component comprises copper and zinc, and in terms of oxide mass fraction, the content of the aluminum support in the catalyst particles is 1-40% by weight, the content of copper is 10-70% by weight, and the content of zinc is 5-60% by weight.

[0025] The method for preparing the catalyst particles includes: mixing and pulping an aluminum hydroxide support with an active ingredient obtained through co-precipitation, washing, and drying; the aluminum hydroxide support is preferably precipitated aluminum hydroxide.

[0026] The copper-based catalyst also includes a binder and optional water;

[0027] Preferably, the copper-based catalyst comprises 92-98% by weight catalyst particles, 1-4% by weight binder, and 1-4% by weight water.

[0028] As a specific embodiment of the present invention, the catalyst is used for methanol production from syngas, methanol production via CO2 hydrogenation, decarbonylation of iron and nickel, desulfurization, butyraldehyde hydrogenation to butanol, octenal hydrogenation to octanol, and cyclohexanol dehydrogenation to cyclohexanone; wherein...

[0029] The catalyst used for methanol production from syngas contains 40.0–60.0% copper, 15.0–25.0% zinc, and 3.0–15.0% aluminum.

[0030] The catalyst used for CO2 hydrogenation to methanol contains 40.0–60.0% copper, 20.0–30.0% zinc, and 5.0–20.0% aluminum.

[0031] The catalyst used for decarbonylation of iron carbonyl nickel contains 20.0–40.0% copper, 20.0–40.0% zinc, and 10.0–30.0% aluminum.

[0032] The catalyst used for desulfurization contains 10.0% to 30.0% by weight of copper, 60.0% to 80.0% by weight of zinc, and 1.0% to 10.0% by weight of aluminum.

[0033] The catalyst used for the hydrogenation of butyraldehyde to butanol contains 20.0%–40.0% by weight of copper, 50.0%–70.0% by weight of zinc, and 5.0%–15.0% by weight of aluminum.

[0034] The catalyst used for the hydrogenation of octenal to octanol contains 20.0%–40.0% by weight of copper, 40.0%–60.0% by weight of zinc, and 2.0%–10.0% by weight of aluminum.

[0035] The catalyst used for the dehydrogenation of cyclohexanol to cyclohexanone contains 20.0%–40.0% by weight of copper, 30.0%–50.0% by weight of zinc, and 5.0%–20.0% by weight of aluminum.

[0036] Secondly, the present invention provides a method for preparing the aforementioned multifunctional copper-based catalyst, comprising the following steps:

[0037] S1: The first alkali compound is used as a precipitant and mixed with a copper-zinc solution for co-precipitation. After aging, the basic precursor is obtained and washed.

[0038] S2: Under ultrasonic conditions, the second alkali compound is used as a precipitant to co-precipitate with the basic precursor mixture obtained in step S1 using copper solution or zinc solution. After precipitation, the mixture is aged and washed to obtain the catalyst precursor.

[0039] S3: The third alkali compound is used as a precipitant to co-precipitate with a soluble aluminum solution. After precipitation, the solution is aged to obtain an aluminum hydroxide carrier.

[0040] S4: Mix the catalyst precursor obtained in step S2 and the aluminum hydroxide support obtained in step S3, stir, heat, age to obtain catalyst slurry, wash, filter, and dry to obtain dry catalyst particles.

[0041] S5: The dry catalyst particles obtained in step S4 are impregnated in a copper-zinc solution or a copper solution or a zinc solution, dried, calcined, and shaped to obtain the copper-based catalyst.

[0042] As a specific embodiment of the present invention, the first alkali compound, the second alkali compound, and the third alkali compound are each independently one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia, sodium hydroxide, and potassium hydroxide, and the alkali concentration is 0.5 mol / L to 5 mol / L, preferably 1 mol / L.

[0043] In a specific embodiment of the present invention, in step S1, the molar ratio of the alkali in the first alkali compound to the copper ions and zinc ions in the copper-zinc solution is (1-3):1, preferably 2:1; the copper ion content in the copper-zinc solution is 10.0 g / L to 20.0 g / L, and the zinc ion content is 10.0 g / L to 20.0 g / L.

[0044] In a specific embodiment of the present invention, in step S2, the molar ratio of the alkali in the second alkali compound to the copper ions in the copper solution or the zinc ions in the zinc solution is (1-3):1, preferably 2:1; the copper ion content in the copper solution is 10.0 g / L to 50.0 g / L, and the zinc ion content in the zinc solution is 10.0 g / L to 60.0 g / L; wherein, the copper ion content in the copper solution used for syngas to methanol is 40 g / L. The copper solution used for CO2 hydrogenation to methanol contains 40.0 g / L to 50.0 g / L of copper ions, and the zinc solution contains 15.0 g / L to 25.0 g / L of zinc ions. The copper solution used for decarbonylation of iron and nickel contains 20.0 g / L to 30.0 g / L of copper ions, and the zinc solution contains 20.0 g / L to 50.0 g / L of zinc ions. 30.0 g / L; the copper ion content in the copper solution used for desulfurization is 10.0 g / L to 20.0 g / L, and the zinc ion content in the zinc solution is 50.0 g / L to 60.0 g / L; the copper ion content in the copper solution used for the hydrogenation of butyraldehyde to butanol is 20.0 g / L to 30.0 g / L, and the zinc ion content in the zinc solution is 40.0 g / L to 60.0 g / L; the copper ion content in the copper solution used for the hydrogenation of octenal to octanol is 20.0 g / L to 30.0 g / L. The zinc ion content in the zinc solution is 30.0 g / L to 50.0 g / L; the copper ion content in the copper solution used for the dehydrogenation of cyclohexanol to cyclohexanone is 20.0 g / L to 30.0 g / L, and the zinc ion content in the zinc solution is 30.0 g / L to 40.0 g / L; the precipitation conditions are a pH of 7.0 to 7.9, a temperature of 50 to 90°C, an aging temperature of 50 to 90°C, and an aging time of 30 min to 120 min.

[0045] In a specific embodiment of the present invention, in step S3, the molar ratio of the alkali in the third alkali compound to the aluminum ions in the soluble aluminum solution is (1-4):1, preferably 3:1; the precipitation conditions include: precipitation temperature of 10-50℃, endpoint pH value of 7.0-7.2, aging temperature of 10-50℃, and aging time of 30-120 min; the soluble aluminum solution includes, but is not limited to, aluminum nitrate, aluminum acetate, and aluminum oxalate, with a solution concentration of 0.5-1.5 mol / L.

[0046] In a specific embodiment of the present invention, in step S4, the mass of aluminum atoms in the aluminum hydroxide support accounts for 1 to 40% of the total mass of the catalyst; the mixing and slurrying conditions include: a temperature of 50 to 90°C, an aging temperature of 50 to 90°C, and an aging time of 30 to 120 minutes.

[0047] In a specific embodiment of the present invention, in step S5, the copper ion content in the copper solution is 20.0 g / L to 70.0 g / L, and the zinc ion content in the zinc solution is 20.0 g / L to 90.0 g / L; wherein, the copper ion content in the copper solution used for syngas to methanol is 60.0 g / L to 70.0 g / L, and the zinc ion content in the zinc solution is 20.0 g / L to 25.0 g / L; the copper ion content in the copper solution used for CO2 hydrogenation to methanol is... The amount of copper used for decarbonylation is 60.0 g / L to 70.0 g / L, and the zinc ion content in the zinc solution is 25.0 g / L to 30.0 g / L; the copper solution used for decarbonylation has a copper ion content of 30.0 g / L to 50.0 g / L, and the zinc solution has a zinc ion content of 40.0 g / L to 50.0 g / L; the copper solution used for desulfurization has a copper ion content of 20.0 g / L to 40.0 g / L, and the zinc solution has a zinc ion content of 80.0 g / L to 90.0 g / L. 0.0 g / L; the copper ion content in the copper solution used for the hydrogenation of butyraldehyde to butanol is 40.0 g / L to 50.0 g / L, and the zinc ion content in the zinc solution is 70.0 g / L to 80.0 g / L; the copper ion content in the copper solution used for the hydrogenation of octenal to octanol is 40.0 g / L to 50.0 g / L, and the zinc ion content in the zinc solution is 60.0 g / L to 70.0 g / L; the copper ion content in the copper solution used for the dehydrogenation of cyclohexanol to cyclohexanone is 40.0 g / L. The zinc ion content in the zinc solution is 50.0 g / L to 60.0 g / L; and / or, the impregnation temperature is 10 to 50°C, and the impregnation time is 1 to 24 hours; and / or, the drying temperature is 80°C to 120°C, and the drying time is 6 to 24 hours; and / or, the calcination temperature is 280°C to 400°C, and the calcination time is 20 to 60 minutes; and / or, the forming method includes tablet forming, extrusion forming, and ball forming.

[0048] As a specific embodiment of the present invention, in step S5, the molding process further includes adding a binder and water as molding aids; the amount of binder added is 1 to 4% by weight of the calcined particles; the amount of water added as molding aid is 1 to 4% by weight of the calcined particles; the binder is one or more of graphite, guar gum powder, diatomaceous earth or cellulose.

[0049] All of the above-mentioned raw materials used in this invention can be prepared in-house or purchased commercially; this invention does not impose any particular limitations on them.

[0050] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0051] 1. The multifunctional copper-based catalyst of the present invention adjusts the content and distribution of active components in the catalyst by changing the amount of raw materials used in the multi-step precipitation and impregnation steps. The copper-based catalysts with different contents of active components can be used in the fields of syngas to methanol, decarbonylation of iron and nickel, desulfurization, CO2 hydrogenation to methanol, butyraldehyde hydrogenation to butanol, octenal hydrogenation to octanol, and cyclohexanol dehydrogenation to cyclohexanone.

[0052] 2. The multifunctional copper-based catalyst of the present invention can achieve the effect of coupling multiple preparation methods without changing the existing catalyst preparation process and equipment. It has the characteristics of low cost, high efficiency and good stability, and has obvious technological advantages.

[0053] 3. The multifunctional copper-based catalyst of the present invention can improve the dispersion of active centers in the catalyst, thereby improving the catalyst activity.

[0054] 4. Compared with traditional methods for preparing catalysts, the multifunctional copper-based catalyst prepared by the method of this invention has advantages such as high activity, strong adaptability, and good thermal stability. Detailed Implementation

[0055] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0056] Example 1

[0057] This embodiment provides a copper-based catalyst and its preparation method, with specific details as follows:

[0058] S1: 1.5 L of 2 mol / L sodium bicarbonate aqueous solution was used as a precipitant and co-precipitated with 1 L of copper-zinc solution containing 20 g / L copper and 10 g / L zinc. The precipitation temperature was 70℃, the pH value during the precipitation process was 7.9, and the final pH value was controlled at 7.2. After the precipitation was completed, the mixture was aged at 70℃ for 30 min to obtain a precursor mixture of the basic catalyst, which was then washed.

[0059] S2: Under ultrasonic conditions, 1.5 L of 5 mol / L sodium carbonate aqueous solution was used as a precipitant and co-precipitated with 1 L of a mixed solution containing 50 g / L copper and 15 g / L zinc into the precursor mixture of the basic catalyst obtained in step S1. The precipitation temperature was 70 °C, the pH value during the precipitation process was 7.8, and the pH value at the precipitation endpoint was controlled at 7.0. After precipitation, the mixture was aged at 70 °C for 60 min to obtain the catalyst precursor mixture. The catalyst precursor mixture was washed, and the conductivity of the solution was controlled at the washing endpoint to be 8 μS / cm to obtain the catalyst precursor.

[0060] S3: Neutralize 1L of 0.5mol / L aluminum nitrate solution with 3L of 0.5mol / L ammonia water as precipitant. The precipitation temperature is 20℃, and the final pH value is controlled at 7.0. After precipitation, age at 20℃ for 30min to obtain aluminum hydroxide carrier.

[0061] S4: Mix 139.3g of the catalyst precursor obtained in step S2 and 39.4g of the aluminum hydroxide support obtained in step S3, stir at 70℃ for 10min, age for 60min to obtain catalyst slurry, wash, filter, and dry at 105℃ for 10h to obtain dry catalyst particles.

[0062] S5: Using the excess impregnation method, the dry catalyst particles obtained in step S4 are impregnated in a copper-zinc solution containing 70 g / L copper and 20 g / L zinc at an impregnation temperature of 20°C for 12 hours. After washing, filtering, drying, and calcining at 350°C for 30 minutes, calcined particles are obtained.

[0063] S6: Add 2% by weight of graphite binder and 2% by weight of water to the calcined particles obtained in step S5, stir evenly, and then form into sheets to obtain copper-based catalyst M1.

[0064] The copper-based catalyst obtained in Example 1 contained 63.0% copper oxide, 22.5% zinc oxide, 10.5% aluminum oxide, 2.0% binder, and 2.0% water.

[0065] Example 2

[0066] This embodiment provides a copper-based catalyst and its preparation method, with specific details as follows:

[0067] S1: 3 L of 1 mol / L potassium bicarbonate was used as a precipitant and co-precipitated with 1 L of a mixed solution containing 10 g / L copper and 20 g / L zinc. The precipitation temperature was 50℃, the pH value was controlled at 7.2 during the precipitation process, and the final pH value was controlled at 7.0. After precipitation, the mixture was aged at 50℃ for 60 min to obtain a precursor mixture of the basic catalyst, which was then washed.

[0068] S2: Under ultrasonic conditions, 0.5 L of 4 mol / L potassium carbonate was used as a precipitant and co-precipitated with 1 L of a copper-zinc solution containing 10 g / L copper and 60 g / L zinc into the precursor mixture of the basic catalyst obtained in step S1. The precipitation temperature was 50 °C, the pH value during the precipitation process was controlled at 7.2, and the final pH value was controlled at 7.0. After precipitation, the mixture was aged at 50 °C for 90 min to obtain the catalyst precursor mixture. The catalyst precursor mixture was washed, and the conductivity of the solution was controlled at the end of the washing process to be 10 μS / cm to obtain the catalyst precursor.

[0069] S3: Neutralize 0.5L of 0.5mol / L aluminum acetate solution with 0.25L of 3mol / L sodium hydroxide as precipitant. The precipitation temperature is 40℃, and the final pH value is controlled at 7.0. After precipitation, age at 40℃ for 120min, wash, filter, and obtain aluminum hydroxide carrier.

[0070] S4: Mix 150.1g of the catalyst precursor obtained in step S3 and 28.3g of the aluminum hydroxide support obtained in step S4, stir at 50℃ for 10min, age for 100min to obtain catalyst slurry, wash, filter, and dry at 100℃ for 20h to obtain dry catalyst particles.

[0071] S5: Using the excess impregnation method, the dry catalyst particles obtained in step S4 are impregnated in a copper-zinc solution containing 20 g / L copper and 90 g / L zinc. The impregnation temperature is 50°C and the impregnation time is 2 hours. After washing, filtering, drying, and calcining at 400°C for 20 minutes, calcined particles are obtained.

[0072] S6: Add 3% by weight of guar gum powder binder and 3% by weight of water to the calcined particles obtained in step S5, stir evenly, and then form into sheets to obtain copper-based catalyst S2.

[0073] The copper-based catalyst obtained in Example 2 contained 8.2% copper oxide, 83.4% zinc oxide, 2.1% aluminum oxide, 3% binder, and 3.0% water.

[0074] Example 3

[0075] This embodiment provides a copper-based catalyst and its preparation method, with specific details as follows:

[0076] S1: 2L of 3mol / L sodium carbonate was used as a precipitant and co-precipitated with 1L of a mixed solution containing 20g / L copper and 10g / L zinc. The precipitation temperature was 80℃, the pH value was controlled at 7.3 during the precipitation process, and the final pH value was controlled at 7.1. After precipitation, the mixture was aged at 80℃ for 40min to obtain a precursor mixture of the basic catalyst, which was then washed.

[0077] S2: Under ultrasonic conditions, 0.8 L of 2.5 mol / L potassium hydroxide was used as a precipitant and co-precipitated with 1 L of a copper-zinc solution containing 50 g / L copper and 25 g / L zinc into the precursor mixture of the basic catalyst obtained in step S1. The precipitation temperature was 80 °C, the pH value during the precipitation process was controlled at 7.2, and the final pH value was controlled at 7.0. After precipitation, the mixture was aged at 80 °C for 30 min to obtain the catalyst precursor mixture. The catalyst precursor mixture was washed, and the conductivity of the solution was controlled at the washing endpoint to be 9 μS / cm to obtain the catalyst precursor.

[0078] S3: Neutralize 1L of 1mol / L aluminum oxalate solution with 0.7L of 1.5mol / L potassium hydroxide as a precipitant. The precipitation temperature is 40℃, and the final pH value is controlled at 7.0. After precipitation, age at 40℃ for 45min to obtain aluminum hydroxide carrier.

[0079] S4: Mix 122.2g of the catalyst precursor obtained in step S2 and 34.0g of the aluminum hydroxide support obtained in step S3, stir at 80℃ for 40min, age for 40min to obtain catalyst slurry, wash, filter, and dry at 90℃ for 24h to obtain dry catalyst particles.

[0080] S5: Using the excess impregnation method, the dry catalyst particles obtained in step S4 are impregnated in a copper-zinc solution containing 70 g / L copper and 25 g / L zinc at a temperature of 40°C for 24 hours. After washing, filtering, drying, and calcining at 330°C for 40 minutes, calcined particles are obtained.

[0081] S6: Add 4% (by weight of calcined particles) of cellulose binder and 3% (by weight of calcined particles) of water to the calcined particles, stir evenly, and then extrude to form copper-based catalyst D3.

[0082] The copper-based catalyst obtained in Example 3 contained 58.2% copper oxide, 23.7% zinc oxide, 11.1% aluminum oxide, 4.0% binder, and 3.0% water.

[0083] Example 4

[0084] This embodiment provides a copper-based catalyst and its preparation method, with specific details as follows:

[0085] S1: 2.5 L of 2 mol / L potassium carbonate aqueous solution was used as a precipitant and co-precipitated with 1 L of copper-zinc solution containing 15 g / L copper and 15 g / L zinc. The precipitation temperature was 60℃, the pH value was controlled at 7.1 during the precipitation process, and the final pH value was controlled at 7.0. After precipitation, the mixture was aged at 60℃ for 50 min to obtain a precursor mixture of the basic catalyst, which was then washed.

[0086] S2: Under ultrasonic conditions, 2L of 1mol / L sodium bicarbonate aqueous solution was used as a precipitant and co-precipitated with 1L of a mixed solution containing 20g / L copper and 25g / L zinc into the precursor mixture of the basic catalyst obtained in step S1. The precipitation temperature was 60℃, the pH value during the precipitation process was 7.5, and the pH value at the precipitation endpoint was controlled at 7.1. After precipitation, the mixture was aged at 60℃ for 110min to obtain the catalyst precursor mixture. The catalyst precursor mixture was washed, and the conductivity of the solution was controlled at the washing endpoint to be 8.5μs / cm to obtain the catalyst precursor.

[0087] S3: Neutralize 3L of 1mol / L aluminum nitrate solution with 2L of 1.0mol / L sodium carbonate as precipitant. The precipitation temperature is 25℃, and the final pH value is controlled at 7.0. After precipitation, age at 25℃ for 50min to obtain aluminum hydroxide carrier.

[0088] S4: Mix 148.0g of the catalyst precursor obtained in step S2 and 19.1g of the aluminum hydroxide support obtained in step S3, stir at 60℃ for 20min, age for 70min to obtain catalyst slurry, wash, filter, and dry at 120℃ for 10h to obtain dry catalyst particles.

[0089] S5: Using the excess impregnation method, the dry catalyst particles obtained in step S4 are impregnated in a copper-zinc solution containing 30 g / L copper and 40 g / L zinc at an impregnation temperature of 40°C for 18 hours. After washing, filtering, drying, and calcining at 280°C for 60 minutes, calcined particles are obtained.

[0090] S6: Add 2% by weight of diatomaceous earth binder and 2% by weight of water to the calcined particles obtained in step S5, stir evenly, and then form into sheets to obtain copper-based catalyst B4.

[0091] The copper-based catalyst obtained in Example 4 contained 33.9% copper oxide, 36.5% zinc oxide, 25.3% aluminum oxide, 2.2% binder, and 2.1% water.

[0092] Example 5

[0093] This embodiment provides a copper-based catalyst and its preparation method, with specific details as follows:

[0094] S1: 0.75 L of 4.0 mol / L sodium hydroxide aqueous solution was used as a precipitant and co-precipitated with 1 L of copper-zinc solution containing 10 g / L copper and 18 g / L zinc. The precipitation temperature was 63℃, the pH value was controlled at 7.4 during the precipitation process, and the final pH value was controlled at 7.0. After precipitation, the mixture was aged at 63℃ for 90 min to obtain a precursor mixture of the basic catalyst, which was then washed.

[0095] S2: Under ultrasonic conditions, 1.67 L of 1.2 mol / L sodium carbonate aqueous solution was used as a precipitant and co-precipitated with 1 L of copper-zinc solution containing 20 g / L copper and 50 g / L zinc into the precursor mixture of the basic catalyst obtained in step S1. The precipitation temperature was 66 °C, the pH value during the precipitation process was controlled at 7.4, and the final pH value was controlled at 7.0. After precipitation, the mixture was aged at 66 °C for 50 min to obtain the catalyst precursor mixture. The catalyst precursor mixture was washed, and the conductivity of the solution was controlled at the washing endpoint to be 10 μS / cm to obtain the catalyst precursor.

[0096] S3: Neutralize 1.2L of 0.8mol / L aluminum oxalate solution with 2.88L of 1.0mol / L potassium bicarbonate as a precipitant. The precipitation temperature is 20℃, and the final pH value is controlled at 7.0. After precipitation, age at 20℃ for 30min to obtain aluminum hydroxide support.

[0097] S4: Mix 154.5g of the catalyst precursor obtained in step S2 and 19.4g of the aluminum hydroxide support obtained in step S3, stir at 70℃ for 15min, age for 60min to obtain catalyst slurry, wash, filter, and dry at 115℃ for 10h to obtain dry catalyst particles.

[0098] S5: Using the excess impregnation method, the dry catalyst particles obtained in step S4 are impregnated in a copper-zinc solution containing 40 g / L copper and 70 g / L zinc at a temperature of 50°C for 22 hours. After washing, filtering, drying, and calcining at 400°C for 20 minutes, calcined particles are obtained.

[0099] S6: Add 1.5% graphite binder and 2.5% water by mass of the calcined particles to the calcined particles obtained in step S5, stir evenly, and then form into sheets to obtain the copper-based catalyst DH5.

[0100] The copper-based catalyst obtained in Example 5 contained 28.9% copper oxide, 61.0% zinc oxide, 6.1% aluminum oxide, 1.5% binder, and 2.5% water.

[0101] Example 6

[0102] This embodiment provides a copper-based catalyst and its preparation method, with specific details as follows:

[0103] S1: A mixed solution of 0.6 L of 2.5 mol / L sodium carbonate and 0.6 L of 2.5 mol / L potassium carbonate was used as a precipitant to co-precipitate with 1 L of a copper-zinc solution containing 10 g / L copper and 16 g / L zinc. The precipitation temperature was 65 °C, the pH value during the precipitation process was controlled at 7.5, and the final pH value was controlled at 7.0. After precipitation, the mixture was aged at 65 °C for 30 min to obtain a precursor mixture of the basic catalyst, which was then washed.

[0104] S2: Under ultrasonic conditions, 0.45 L of 4.5 mol / L sodium bicarbonate aqueous solution was used as a precipitant and co-precipitated with 1 L of a mixed solution containing 20 g / L copper and 40 g / L zinc into the precursor mixture of the basic catalyst obtained in step S1. The precipitation temperature was 65 °C, the pH value during the precipitation process was 7.5, and the pH value at the precipitation endpoint was controlled at 7.0. After precipitation, the mixture was aged at 65 °C for 35 min to obtain the catalyst precursor mixture. The catalyst precursor mixture was washed, and the conductivity of the solution was controlled at the washing endpoint to be 9.5 μs / cm to obtain the catalyst precursor.

[0105] S3: Neutralize 1L of 0.4mol / L aluminum nitrate solution with 1.2L of 1.0mol / L potassium bicarbonate as a precipitant. The precipitation temperature is 15℃, and the final pH value is controlled at 7.0. After precipitation, age at 15℃ for 40min to obtain aluminum hydroxide support.

[0106] S4: Mix 129.9g of the catalyst precursor obtained in step S2 and 12.0g of the aluminum hydroxide support obtained in step S3, stir at 65℃ for 20min, age for 80min to obtain catalyst slurry, wash, filter, and dry at 100℃ for 12h to obtain dry catalyst particles.

[0107] S5: Using the excess impregnation method, the dry catalyst particles obtained in step S4 are impregnated in a copper-zinc solution containing 40 g / L copper and 60 g / L zinc at a temperature of 30°C for 12 hours. After washing, filtering, drying, and calcining at 340°C for 40 minutes, calcined particles are obtained.

[0108] S6: Add 2.5% graphite binder and 2.2% water by mass of the calcined particles to the calcined particles obtained in step S5, stir evenly, and then form into sheets to obtain copper-based catalyst X6.

[0109] The copper-based catalyst obtained in Example 6 contained 34.6% copper oxide, 57.4% zinc oxide, 3.3% aluminum oxide, 2.5% binder, and 2.2% water.

[0110] Example 7

[0111] This embodiment provides a copper-based catalyst and its preparation method, with specific details as follows:

[0112] S1: 1.4 L of 2.2 mol / L potassium bicarbonate was used as a precipitant and co-precipitated with 1 L of copper-zinc solution containing 10 g / L copper and 14 g / L zinc. The precipitation temperature was 60℃, the pH value was controlled at 8.0 during the precipitation process, and the final pH value was controlled at 7.5. After the precipitation was completed, the mixture was aged at 60℃ for 40 min to obtain a precursor mixture of the basic catalyst, which was then washed.

[0113] S2: Under ultrasonic conditions, 0.59 L of 3.5 mol / L sodium carbonate aqueous solution was used as a precipitant and co-precipitated with 1 L of copper-zinc solution containing 20 g / L copper and 30 g / L zinc into the precursor mixture of the basic catalyst obtained in step S1. The precipitation temperature was 60 °C, the pH value during the precipitation process was 7.8, and the pH value at the precipitation endpoint was controlled at 7.0. After precipitation, the mixture was aged at 60 °C for 60 min to obtain the catalyst precursor mixture. The catalyst precursor mixture was washed, and the conductivity of the solution was controlled at the washing endpoint to be 7 μs / cm to obtain the catalyst precursor.

[0114] S3: Neutralize 0.8L of 1.0mol / L aluminum nitrate solution with 1L of 2.5mol / L sodium bicarbonate as a precipitant. The precipitation temperature is 10℃, and the final pH value is controlled at 7.0. After precipitation, age at 10℃ for 30min to obtain aluminum hydroxide support.

[0115] S4: Mix 119.7g of the catalyst precursor obtained in step S2 and 12.4g of the aluminum hydroxide support obtained in step S3, stir at 60℃ for 30min, age for 70min to obtain catalyst slurry, wash, filter, and dry at 100℃ for 12h to obtain dry catalyst particles.

[0116] S5: Using the excess impregnation method, the dry catalyst particles obtained in step S4 are impregnated in a mixed solution containing 40 g / L copper and 50 g / L zinc at a temperature of 40°C for 24 hours. After washing, filtering, drying, and calcining at 280°C for 120 minutes, calcined particles are obtained.

[0117] S6: Add 3.1% by weight of guar gum powder binder and 3.0% by weight of water to the calcined particles obtained in step S5, stir evenly, and then form into sheets to obtain copper-based catalyst H7.

[0118] The copper-based catalyst obtained in Example 7 contained 37.6% copper oxide, 49.1% zinc oxide, 7.2% aluminum oxide, 3.1% binder, and 3.0% water.

[0119] Comparative Example 1

[0120] This comparative example provides a catalyst and its preparation method, the details of which are as follows:

[0121] S1: Heat 1L of solution A containing 115g Cu(NO3)2 and 40g Zn(NO3)2 to 70℃ and set aside for later use;

[0122] S2: Dissolve 150g NaHCO3 in 1.80L of deionized water to prepare solution B, and heat to 70℃ for later use;

[0123] S3: Add solution A to solution B under stirring. The neutralization process is controlled at 70℃ and the final pH value is controlled at 7.0. After color change and aging, wash, add 11.5g of alumina support, and after washing, filtering, drying, calcining and molding, copper-based methanol synthesis catalyst R1 is obtained.

[0124] The catalyst obtained in Comparative Example 1 contained 62.8% copper oxide, 22.2% zinc oxide, 9.8% aluminum oxide, 2.8% binder, and 2.4% water.

[0125] Comparative Example 2

[0126] This comparative example provides a catalyst and its preparation method, the details of which are as follows:

[0127] S1: Heat 1L of solution A containing 35g Cu(NO3)2 and 350g Zn(NO3)2 to 90℃ and set aside for later use;

[0128] S2: Dissolve 400g NaHCO3 in 3.8L of deionized water to prepare solution B, and heat to 86℃ for later use;

[0129] S3: Add solution A to solution B under stirring. The temperature during the neutralization process is controlled at 85℃, and the final pH value is controlled at 6.5. After color change and aging, wash, add 6.0g of alumina support, and after washing, filtering, drying, calcining and molding processes, copper-based methanol synthesis catalyst R2 is obtained.

[0130] The catalyst obtained in Comparative Example 2 contained 8.3% copper oxide, 83.8% zinc oxide, 2.2% aluminum oxide, 2.9% binder, and 2.8% water.

[0131] Comparative Example 3

[0132] This comparative example provides a catalyst and its preparation method, the details of which are as follows:

[0133] S1: Heat 1L of solution A containing 140g Cu(NO3)2 and 55.8g Zn(NO3)2 to 65℃ and set aside for later use;

[0134] S2: Dissolve 215g NaHCO3 in 2.6L of deionized water to prepare solution B, and heat to 70℃ for later use;

[0135] S3: Solution A is added to solution B under stirring. The temperature during the neutralization process is controlled at 68℃, and the final pH value is controlled at 7.2. After color change and aging, the solution is washed, and 16.4g of alumina support is added. After washing, filtering, drying, calcining, and molding, copper-based methanol synthesis catalyst R3 is obtained.

[0136] The catalyst obtained in Comparative Example 3 contained 59.4% copper oxide, 24.0% zinc oxide, 10.9% aluminum oxide, 2.8% binder, and 2.9% water.

[0137] Comparative Example 4

[0138] This comparative example provides a catalyst and its preparation method, the details of which are as follows:

[0139] S1: Heat 1L of solution A containing 80g Cu(NO3)2 and 85g Zn(NO3)2 to 80℃ and set aside for later use;

[0140] S2: Dissolve 276g NaHCO3 in 4.5L of deionized water to prepare solution B, and heat to 80℃ for later use;

[0141] S3: Add solution A to solution B under stirring. The neutralization process is controlled at 80℃ and the final pH value is controlled at 7.1. After color change and aging, wash, add 38g of alumina support, and after washing, filtering, drying, calcining and molding processes, copper-based methanol synthesis catalyst R4 is obtained.

[0142] The catalyst obtained in Comparative Example 4 contained 34.1% copper oxide, 36.8% zinc oxide, 25.2% aluminum oxide, 2.0% binder, and 1.9% water.

[0143] Comparative Example 5

[0144] This comparative example provides a catalyst and its preparation method, the details of which are as follows:

[0145] S1: Heat 1L of solution A containing 51.4g Cu(NO3)2 and 105g Zn(NO3)2 to 70℃ and set aside for later use;

[0146] S2: Dissolve 182g NaHCO3 in 2.2L of deionized water to prepare solution B, and heat to 70℃ for later use;

[0147] S3: Add solution A to solution B under stirring. The neutralization process is controlled at 70℃ and the final pH value is controlled at 7.5. After color change and aging, wash, add 6.8g of alumina support, and after washing, filtering, drying, calcining and molding, copper-based methanol synthesis catalyst R5 is obtained.

[0148] The catalyst obtained in Comparative Example 5 contained 29.2% copper oxide, 60.6% zinc oxide, 6.0% aluminum oxide, 1.8% binder, and 2.4% water.

[0149] Comparative Example 6

[0150] This comparative example provides a catalyst and its preparation method, the details of which are as follows:

[0151] S1: Heat 1L of solution A containing 67.1g Cu(NO3)2 and 110g Zn(NO3)2 to 60℃ and set aside for later use;

[0152] S2: Dissolve 171g of NaHCO3 in 2L of deionized water to prepare solution B, and heat to 60℃ for later use;

[0153] S3: Add solution A to solution B under stirring. Control the temperature at 60℃ during the neutralization process and control the final pH value to 7.0. After color change and aging, wash, add 4.0g of alumina support, and then proceed with washing, filtration, drying, calcination, and molding processes to obtain copper-based methanol synthesis catalyst R6.

[0154] The catalyst obtained in Comparative Example 6 contained 34.5% copper oxide, 57.4% zinc oxide, 3.2% aluminum oxide, 2.5% binder, and 2.4% water.

[0155] Comparative Example 7

[0156] This comparative example provides a catalyst and its preparation method, the details of which are as follows:

[0157] S1: Heat 1L of solution A containing 85g Cu(NO3)2 and 110g Zn(NO3)2 to 72℃ and set aside for later use;

[0158] S2: Dissolve 161g of NaHCO3 in 2L of deionized water to prepare solution B, and heat to 72℃ for later use;

[0159] S3: Add solution A to solution B under stirring. The neutralization process is controlled at 72℃ and the final pH value is controlled at 7.5. After color change and aging, wash, add 10g of alumina support, and after washing, filtering, drying, calcining and molding processes, copper-based methanol synthesis catalyst R7 is obtained.

[0160] The catalyst obtained in Comparative Example 7 contained 37.7% copper oxide, 49.5% zinc oxide, 6.9% aluminum oxide, 3.1% binder, and 2.8% water.

[0161] Test case

[0162] Activity testing of catalysts D3 and R3: A micro-fixed-bed continuous flow reactor was used. The catalyst loading was 3g, with a particle size of 16-40 mesh. Catalyst reduction was performed in an H2 (H2:N2 = 5:95) atmosphere with a programmed temperature increase (20℃ / h) for 10 hours, reaching a temperature of 230℃. The reducing gas was then switched to the feed gas for activity testing. The activity testing conditions were a reaction pressure of 5.0 MPa and a space velocity of 10000 h⁻¹. -1 The temperature was 230℃, and the synthesis gas composition was: CO2: 23%, H2: 69%, balance N2 (v / v). After the reaction stabilized for 2 hours, the liquid in the liquid collector was vented and timing was started. The collector was cooled with circulating water. After 2.5 hours, the liquid in the collector (crude methanol) was collected, weighed, and quantitatively analyzed by chromatography to calculate the methanol space-time yield. The methanol content in the liquid product was analyzed using an Agilent-7890 gas chromatograph. The chromatographic conditions were: flame ionization detector (FID), HP-INNOWax column (60m long, 0.32mm inner diameter, 0.5μm wall thickness), programmed temperature rise, nitrogen as carrier gas, injection port temperature 250℃, constant pressure 10psi, split mode 10:1, detection chamber temperature 300℃, hydrogen flow rate 30mL / min, air flow rate 400mL / min, and make-up flow rate 25mL / min. External standard method was used for quantification.

[0163] Activity testing of catalysts M1 and R1: A micro fixed-bed continuous flow reactor was used. The catalyst loading was 3g, with a particle size of 16-40 mesh. Catalyst reduction was performed in an H2 (H2:N2 = 5:95) atmosphere with a programmed temperature increase (20℃ / h) for 10 hours, reaching a temperature of 230℃. The reducing gas was then switched to the feed gas for activity testing. The activity testing conditions were a reaction pressure of 5.0 MPa and a space velocity of 10000 h⁻¹. -1 The temperature was 230℃, and the synthesis gas composition was: CO: 14%, CO2: 4%, H2: 70%, with the balance being N2 (v / v). After the reaction stabilized for 2 hours, the liquid in the liquid collector was vented and timing was started. The collector was cooled with circulating water. After 2.5 hours, the liquid in the collector (crude methanol) was collected, weighed, and quantitatively analyzed by chromatography to calculate the methanol space-time yield. The methanol content in the liquid product was analyzed using an Agilent-7890 gas chromatograph. The chromatographic conditions were: flame ionization detector (FID), HP-INNOWax column (60m long, 0.32mm inner diameter, 0.5μm wall thickness), programmed temperature rise, nitrogen as carrier gas, injection port temperature 250℃, constant pressure 10psi, split mode 10:1, detection chamber temperature 300℃, hydrogen flow rate 30mL / min, air flow rate 400mL / min, and make-up flow rate 25mL / min. External standard method was used for quantification.

[0164] Activity testing of catalysts S2 and R2: A micro-fixed-bed continuous flow reactor was used. The catalyst loading was 3 g, with a particle size of 16-40 mesh, and the temperature was raised to 230℃. The activity testing conditions were a reaction pressure of 5.0 MPa and a space velocity of 10000 h⁻¹. -1 The temperature was 230℃, and the composition of the synthesis gas was: CO: 14%, CO2: 4%, H2: 70%, balance N2 (v / v), S 10ppm. After 12h of reaction, the S content in the catalyst before and after the reaction was measured.

[0165] Activity testing of catalysts B4 and R4: A micro-fixed-bed continuous flow reactor was used. The catalyst loading was 3g, with a particle size of 16-40 mesh. Catalyst reduction was performed in an H2 (H2:N2 = 5:95) atmosphere with a programmed temperature increase (20℃ / h) for 10 hours, reaching a temperature of 230℃. The reducing gas was then switched to the feed gas for activity testing. The activity testing conditions were a reaction pressure of 5.0 MPa and a space velocity of 10000 h⁻¹. -1 The temperature was 230℃, the composition of the synthesis gas was: CO: 14%, CO2: 4%, H2: 70%, balance N2 (v / v), Fe(CO) 510ppm. After 12h of reaction, the Fe content in the catalyst before and after the reaction was measured.

[0166] Activity testing of catalysts DH5 and R5: A micro fixed-bed continuous flow reactor was used. The catalyst loading was 50 g, with a particle size of 16-40 mesh. Catalyst reduction was performed in an H2 (H2:N2 = 5:95) atmosphere with a programmed temperature increase (20℃ / h) for 10 hours, reaching a temperature of 230℃. The reducing gas was then switched to the feed gas for activity testing. The activity testing conditions were a reaction pressure of 0.3 MPa and a liquid hourly space velocity (LHSV) of 0.36 h⁻¹. -1 The reaction was carried out at 200℃, using analytical grade n-butyraldehyde as the raw material. After the reaction stabilized for 2 hours, the liquid in the liquid collector was vented and timing was started. The collector was cooled with circulating water. After 2.5 hours, the liquid in the collector (crude butanol) was collected, weighed, and quantitatively analyzed by chromatography to calculate the n-butyraldehyde conversion rate and n-butanol selectivity. The n-butyraldehyde and butanol content in the liquid product was analyzed using an Agilent-7890 gas chromatograph. The chromatographic conditions were: flame ionization detector (FID), HP-INNOWax column (60m long, 0.32mm inner diameter, 0.5μm wall thickness), programmed temperature rise, nitrogen as carrier gas, injection port temperature 250℃, constant pressure 10psi, split mode 10:1, detection chamber temperature 300℃, hydrogen flow rate 30mL / min, air flow rate 400mL / min, and make-up flow rate 25mL / min. External standard method was used for quantification.

[0167] Activity testing of catalysts X6 and R6: A micro fixed-bed continuous flow reactor was used. The catalyst loading was 50 g, with a particle size of 16-40 mesh. Catalyst reduction was performed in an H2 (H2:N2 = 5:95) atmosphere with a programmed temperature increase (20℃ / h) for 10 hours, reaching a temperature of 230℃. The reducing gas was then switched to the feed gas for activity testing. The activity testing conditions were a reaction pressure of 0.3 MPa and a liquid hourly space velocity of 0.36 h⁻¹. -1 The reaction was carried out at 230℃, using analytical grade octenal as the raw material. After the reaction stabilized for 2 hours, the liquid in the liquid collector was vented and timing was started. The collector was cooled with circulating water. After 2.5 hours, the liquid in the collector (crude octanol) was collected, weighed, and subjected to chromatographic quantitative analysis to calculate the octenal conversion rate and octanol selectivity. The octenal and octanol contents in the liquid product were analyzed using an Agilent-7890 gas chromatograph. The chromatographic conditions were: flame ionization detector (FID), HP-INNOWax column (60m long, 0.32mm inner diameter, 0.5μm wall thickness), programmed temperature rise, nitrogen as carrier gas, injection port temperature 250℃, constant pressure 10psi, split mode 10:1, detection chamber temperature 300℃, hydrogen flow rate 30mL / min, air flow rate 400mL / min, and make-up flow rate 25mL / min. External standard method was used for quantification.

[0168] Activity testing of catalysts H7 and R7: A micro fixed-bed continuous flow reactor was used. The catalyst loading was 50 g, with a particle size of 16-40 mesh. Catalyst reduction was performed in an H2 (H2:N2 = 5:95) atmosphere, with a programmed temperature increase (20℃ / h) for 12 hours, reaching a temperature of 230℃. The reducing gas was then switched to the feed gas for activity testing. The activity testing conditions were a reaction pressure of 0.1 MPa and a liquid hourly space velocity (LHSV) of 0.6 h⁻¹. -1 The reaction was carried out at 230℃ using analytical grade cyclohexanol as the raw material. After stabilizing for 2 hours, the liquid in the liquid collector was vented and timing was started. The collector was cooled with circulating water. After 2.5 hours, the liquid in the collector (a mixture of cyclohexanol and cyclohexanone) was collected, weighed, and quantitatively analyzed by chromatography. The conversion rate of cyclohexanol and the selectivity of cyclohexanone were calculated. The contents of cyclohexanol and cyclohexanone in the liquid product were analyzed using an Agilent-7890 gas chromatograph. The chromatographic conditions were: flame ionization detector (FID), HP-INNOWax column (60 m long, 0.32 mm inner diameter, 0.5 μm wall thickness), programmed temperature rise, nitrogen as carrier gas, injection port temperature 250℃, constant pressure 10 psi, split mode 10:1, detection chamber temperature 300℃, hydrogen flow rate 30 mL / min, air flow rate 400 mL / min, and make-up flow rate 25 mL / min. External standard method was used for quantification.

[0169] The activity test results are shown in Table 1:

[0170] Table 1 Catalyst activity and activity decay

[0171]

[0172] As can be seen from Table 1, the catalyst prepared by the method of the present invention has significantly higher activity than the reference catalyst, and its activity decay rate after 100 hours is lower than that of the reference catalyst.

[0173] The physicochemical parameters of the catalysts prepared in the examples and comparative examples were tested, and the results are shown in Table 2.

[0174] Table 2. Physicochemical characterization results of the catalyst

[0175]

[0176]

[0177] The data in Table 2 show that the catalyst prepared by the method of the present invention has a larger specific surface area and pore volume, indicating that the catalyst sample prepared by the present invention has higher activity, better stability, and longer service life, and can meet higher industrial production requirements.

[0178] In summary, the copper-based catalyst of this invention modifies the content and distribution of active components in the catalyst through multiple precipitation and impregnation steps, achieving the goal of preparing multiple functional catalysts with a single method. This invention can improve the dispersion of active sites in the catalyst, thereby enhancing catalyst activity. Compared with catalysts prepared by traditional methods, the catalyst prepared by this invention has advantages such as high activity, strong adaptability, and good thermal stability.

[0179] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50-90, in this specification it means specifically listing values ​​such as 51-89, 52-88… and 69-71 and 70-71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0180] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing a multifunctional copper-based catalyst, characterized in that, Includes the following steps: S1: The first alkaline compound is used as a precipitant and mixed with a copper-zinc solution for co-precipitation. After aging, a basic precursor mixture is obtained and washed. S2: Under ultrasonic conditions, the second alkali compound is used as a precipitant and co-precipitated with the copper-zinc solution in the basic precursor mixture obtained in step S1. After precipitation, the mixture is aged and washed to obtain the catalyst precursor. S3: The third alkali compound is used as a precipitant to co-precipitate with a soluble aluminum solution. After precipitation, the solution is aged to obtain an aluminum hydroxide carrier. S4: Mix the catalyst precursor obtained in step S2 and the aluminum hydroxide support obtained in step S3, stir, heat, age to obtain catalyst slurry, wash, filter, and dry to obtain dry catalyst particles. S5: The dry catalyst particles obtained in step S4 are impregnated in a copper-zinc solution or a copper solution or a zinc solution, dried, calcined, and shaped to obtain catalyst particles. The copper-based catalyst comprises catalyst particles, the catalyst particles comprising an aluminum support and an active component supported on the aluminum support, wherein the active component comprises copper and zinc. Based on the mass fraction of oxides, the content of the aluminum support in the catalyst particles is 1-40% by weight, the content of copper is 10-70% by weight, and the content of zinc is 5-60% by weight. The copper-based catalyst also includes a binder and, optionally, water.

2. The preparation method according to claim 1, characterized in that, The copper-based catalyst comprises 92-98% by weight of the catalyst particles, 1-4% by weight of the binder, and 1-4% by weight of the water.

3. The preparation method according to claim 1, characterized in that, This catalyst is used for methanol production from syngas, methanol production via CO2 hydrogenation, decarbonylation of iron and nickel, desulfurization, butyraldehyde hydrogenation to butanol, octenal hydrogenation to octanol, and cyclohexanol dehydrogenation to cyclohexanone; among these applications... The catalyst used for methanol production from syngas contains 40.0–60.0% copper, 15.0–25.0% zinc, and 3.0–15.0% aluminum by weight. The catalyst used for CO2 hydrogenation to methanol contains 40.0~60.0% by weight of copper, 20.0~30.0% by weight of zinc, and 5.0~20.0% by weight of aluminum. The catalyst used for decarbonylation of iron carbonyl nickel contains 20.0~40.0% by weight of copper, 20.0~40.0% by weight of zinc, and 10.0~30.0% by weight of aluminum. The catalyst used for desulfurization contains 10.0%~30.0% by weight of copper, 60.0%~80.0% by weight of zinc, and 1.0%~10.0% by weight of aluminum. The catalyst used for the hydrogenation of butyraldehyde to butanol contains 20.0%~40.0% by weight of copper, 50.0%~70.0% by weight of zinc, and 5.0%~15.0% by weight of aluminum. The catalyst used for the hydrogenation of octenal to octanol contains 20.0%~40.0% by weight of copper, 40.0%~60.0% by weight of zinc, and 2.0%~10.0% by weight of aluminum. The catalyst used for the dehydrogenation of cyclohexanol to cyclohexanone contains 20.0% to 40.0% by weight of copper, 30.0% to 50.0% by weight of zinc, and 5.0% to 20.0% by weight of aluminum.

4. The preparation method according to claim 1, characterized in that, The first alkali compound, the second alkali compound, and the third alkali compound are each independently one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia, sodium hydroxide, and potassium hydroxide. In steps S1 to S3, the alkali concentration of the precipitant is independently 0.5 mol / L to 5 mol / L.

5. The preparation method according to any one of claims 1-4, characterized in that, In step S1, the molar ratio of the alkali in the first alkali compound to the copper ions and zinc ions in the copper-zinc solution is (1~3):1; And / or, the copper ion content in the copper-zinc solution is 10.0 g / L to 20.0 g / L, and the zinc ion content is 10.0 g / L to 20.0 g / L.

6. The preparation method according to claim 5, characterized in that, In step S1, the molar ratio of the alkali in the first alkali compound to the copper ions and zinc ions in the copper-zinc solution is 2:

1.

7. The preparation method according to any one of claims 1-4, characterized in that, In step S2, the molar ratio of the alkali in the second alkali compound to the copper ions in the copper-zinc solution or the zinc ions in the copper-zinc solution is (1~3):1; And / or, the copper ion content in the copper-zinc solution is 10.0 g / L to 50.0 g / L, and the zinc ion content in the copper-zinc solution is 10.0 g / L to 60.0 g / L; wherein, The copper ion content in the copper-zinc solution used for methanol production from syngas is 40.0 g / L to 50.0 g / L, and the zinc ion content in the copper-zinc solution is 10.0 g / L to 20.0 g / L. The copper ion content in the copper-zinc solution used for CO2 hydrogenation to methanol is 40.0 g / L to 50.0 g / L, and the zinc ion content in the copper-zinc solution is 15.0 g / L to 25.0 g / L. The copper-zinc solution used for decarbonylation of iron carbonyl nickel contains 20.0 g / L to 30.0 g / L of copper ions and 20.0 g / L to 30.0 g / L of zinc ions. The copper ion content in the copper-zinc solution used for desulfurization is 10.0 g / L to 20.0 g / L, and the zinc ion content in the copper-zinc solution is 50.0 g / L to 60.0 g / L. The copper ion content in the copper-zinc solution used for the hydrogenation of butyraldehyde to butanol is 20.0 g / L to 30.0 g / L, and the zinc ion content in the copper-zinc solution is 40.0 g / L to 60.0 g / L. The copper ion content in the copper-zinc solution used for the hydrogenation of octenal to octanol is 20.0 g / L to 30.0 g / L, and the zinc ion content in the copper-zinc solution is 30.0 g / L to 50.0 g / L. The copper ion content in the copper-zinc solution used for the dehydrogenation of cyclohexanol to cyclohexanone is 20.0 g / L to 30.0 g / L, and the zinc ion content in the copper-zinc solution is 30.0 g / L to 40.0 g / L. And / or, the precipitation conditions are a pH of 7.0 to 7.9, a temperature of 50 to 90°C, an aging temperature of 50 to 90°C, and an aging time of 30 to 120 minutes.

8. The preparation method according to claim 7, characterized in that, In step S2, the molar ratio of the alkali in the second alkali compound to the copper ions in the copper-zinc solution or the zinc ions in the copper-zinc solution is 2:

1.

9. The preparation method according to any one of claims 1-4, characterized in that, In step S3, the molar ratio of the alkali in the third alkali compound to the aluminum ions in the soluble aluminum solution is (1~4):1; And / or, the precipitation conditions include: precipitation temperature of 10~50℃, endpoint pH value of 7.0~7.2, aging temperature of 10~50℃, and aging time of 30min~120min; And / or, the soluble aluminum solution includes one or more of aluminum nitrate, aluminum acetate, and aluminum oxalate, with a solution concentration of 0.5~1.5 mol / L.

10. The preparation method according to claim 9, characterized in that, In step S3, the molar ratio of the alkali in the third alkali compound to the aluminum ions in the soluble aluminum solution is 3:

1.

11. The preparation method according to any one of claims 1-4, characterized in that, In step S4, the aluminum atoms in the aluminum hydroxide support account for 1-40% of the total mass of the catalyst. And / or, the mixing and pulping conditions include: a temperature of 50~90℃, an aging temperature of 50~90℃, and an aging time of 30min~120min.

12. The preparation method according to any one of claims 1-4, characterized in that, In step S5, the copper ion content in the copper solution is 20.0 g / L to 70.0 g / L, and the zinc ion content in the zinc solution is 20.0 g / L to 90.0 g / L; wherein, The copper solution used for methanol production from syngas has a copper ion content of 60.0 g / L to 70.0 g / L, and the zinc solution has a zinc ion content of 20.0 g / L to 25.0 g / L. The copper solution used for CO2 hydrogenation to methanol has a copper ion content of 60.0 g / L to 70.0 g / L, and the zinc solution has a zinc ion content of 25.0 g / L to 30.0 g / L. The copper solution used for decarbonylation of iron carbonyl nickel has a copper ion content of 30.0 g / L to 50.0 g / L, and the zinc solution has a zinc ion content of 40.0 g / L to 50.0 g / L. The copper solution used for desulfurization has a copper ion content of 20.0 g / L to 40.0 g / L, and the zinc solution has a zinc ion content of 80.0 g / L to 90.0 g / L. The copper solution used for the hydrogenation of butyraldehyde to butanol has a copper ion content of 40.0 g / L to 50.0 g / L, and the zinc solution has a zinc ion content of 70.0 g / L to 80.0 g / L. The copper solution used for the hydrogenation of octenal to octanol has a copper ion content of 40.0 g / L to 50.0 g / L, and the zinc solution has a zinc ion content of 60.0 g / L to 70.0 g / L. The copper solution used for the dehydrogenation of cyclohexanol to cyclohexanone has a copper ion content of 40.0 g / L to 50.0 g / L, and the zinc solution has a zinc ion content of 50.0 g / L to 60.0 g / L. And / or, the impregnation temperature is 10~50℃, and the impregnation time is 1~24 hours; and / or, the drying temperature is 80℃-120℃, and the drying time is 6~24 hours; and / or, the calcination temperature is 280℃-400℃, and the calcination time is 20~60 minutes; and / or, the forming method includes sheet forming, extrusion forming, and ball forming.

13. The preparation method according to any one of claims 1-4, characterized in that, In step S5, the molding process also includes adding binder and water as molding aids; The amount of binder added is 1-4% by weight of the calcined particles; the amount of water added as a molding aid is 1-4% by weight of the calcined particles. The binder is one or more of graphite, guar gum, diatomaceous earth, or cellulose.

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