A water-saving, energy-saving, and environmentally friendly copper-based catalyst, its preparation method, and its application.

Abstract

This invention discloses a water-saving, energy-saving, and environmentally friendly copper-based catalyst, its preparation method, and its application. The preparation method includes stirring and mixing copper hydroxide and a support, followed by drying to obtain the water-saving, energy-saving, and environmentally friendly copper-based catalyst. Under the conditions of less than 2 mL of water consumption per gram of catalyst, no waste gas or waste liquid generation, and a total process temperature below 250℃, this invention prepares a catalyst containing highly dispersed copper oxide species. Furthermore, the preparation method is simple, requires minimal equipment, consumes little water, is energy-saving and environmentally friendly, and uses inexpensive and readily available raw materials, thus showing promising prospects for industrial application.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation technology, and specifically relates to a water-saving, energy-saving and environmentally friendly copper-based catalyst, its preparation method and application. Background Technology

[0002] Because of its low price and the high performance of copper-based catalysts in many catalytic reactions, copper-based catalysts are widely used in many catalytic reactions. However, copper-based catalysts have inherent drawbacks. First, the small-diameter metallic copper nanoparticles, which serve as the catalytic active centers, have poor thermal stability. To overcome this defect, current methods for preparing copper-based catalysts typically require high-temperature (>350℃) calcination or reduction treatment. This often leads to the sintering and agglomeration of copper particles in the product catalyst, potentially damaging the original high performance of the copper-based catalyst. Second, the current industrial production method for copper-based catalysts is mainly precipitation. This method has significant drawbacks, primarily the large amount of water used and the high energy consumption of the production equipment. Precipitation requires not only a large amount of alkaline precipitant but also a large amount of water. Finally, a large amount of nitrate is removed through washing, resulting in the generation of tens or even hundreds of tons of wastewater for every ton of catalyst produced. Third, since the raw materials for preparing copper-based catalysts contain nitrates and / or carbonates, the calcination exhaust gas inevitably contains toxic and harmful gases such as nitrogen oxides and carbon oxides, increasing the burden of exhaust gas treatment.

[0003] Patent CN104437488B discloses a method for preparing a catalyst for the gas-phase dehydrogenation of cyclohexanol to cyclohexanone. The catalyst's main component is Cu / SiO2. The catalyst is prepared using a stepwise precipitation method, in which a precipitant is precipitated with silica sol, followed by the addition of copper nitrate solution. The precipitate is then washed, separated from its liquid state, dried, calcined, and finally pressed into tablets. This method requires a washing operation, and the catalyst is calcined at a temperature of 350℃ to 450℃.

[0004] Patent CN113856708A discloses a copper-based catalyst for the catalytic oxidation of hydrogen chloride to chlorine and its preparation method. The method involves dissolving copper chloride and rare earth chlorides in water, adding boehmite and stirring until homogeneous, then adding potassium hydroxide solution dropwise to form a precipitate, washing, shaping, drying, and calcining at 400–550°C in an oxygen-containing atmosphere for 3–8 hours.

[0005] Xiao Fengshou et al. (J.Am.Chem.Soc.,2012,134,15173-15176) reported a solventless method for obtaining a series of M-ZSM-5 (M=Si,Al,Fe,Ga or B) by mechanically mixing NaSiO3·9H2O (SiO2,20wt.%), silica, tetrapropylammonium bromide solution, ammonium chloride and other raw materials (boehmite, Fe(NO3)3·9H2O, Ga2O3 or H3BO3) and then processing them in a reactor at 180°C.

[0006] Yu et al. (Angew., 2020, 59, 2-11) reported that a Pt-encapsulated silicalite-1 molecular sieve catalyst was prepared by direct hydrothermal synthesis in the presence of ethylenediamine ligands. Then, the catalyst without air calcination was directly reduced in a pure H2 atmosphere at 400℃ to prepare a Pt@silicalite-1 catalyst with Pt nanoclusters encapsulated in the pores of the silicalite-1 molecular sieve.

[0007] To address the aforementioned problems, this invention provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, its preparation method, and its application. In the preparation process of this invention, no carbonate or nitrate raw materials (including precipitants such as urea, sodium carbonate, and sodium bicarbonate) are used. The prepared catalyst contains almost no nitrogen or carbon, with only a small amount of water vapor as a byproduct. More importantly, this invention can utilize the reduction and activation treatment step commonly performed in most reaction devices when using fresh catalysts to directly reduce catalysts that have not undergone high-temperature (>250℃) treatment, thus completing the preparation of a highly active copper-based catalyst. Summary of the Invention

[0008] The purpose of this invention is to solve the above-mentioned technical problems and provide a water-saving, energy-saving, and environmentally friendly copper-based catalyst, its preparation method, and its application. The preparation method of this invention produces a high-performance, water-saving, energy-saving, and environmentally friendly copper-based catalyst for the hydrogenation and dehydrogenation catalysis of organic compounds. Furthermore, this invention, through a simple mixing and drying preparation method, can effectively enhance the bonding strength between the active species copper hydroxide and the support, fundamentally avoiding the sintering and agglomeration of metal nanoparticles at high temperatures (>350℃). The entire preparation process is carried out below 250℃, requiring minimal equipment and saving energy and electricity. Moreover, the preparation method of this invention does not use a precipitant, does not introduce nitrogen or carbon components, and requires no form of washing treatment. The preparation method of this invention only emits a small amount of water vapor and generates no liquid wastewater. Therefore, the water consumption for preparing each gram of water-saving, energy-saving, and environmentally friendly copper-based catalyst is less than 2 mL, demonstrating water-saving effects.

[0009] To solve the above-mentioned technical problems, the first aspect of the present invention provides a method for preparing a water-saving, energy-saving and environmentally friendly copper-based catalyst, comprising stirring and mixing copper hydroxide and a support, and then drying to obtain the water-saving, energy-saving and environmentally friendly copper-based catalyst.

[0010] According to some embodiments of the present invention, the support comprises zinc hydroxide or a silicon source. The radii of divalent zinc ions and divalent copper ions (0.74 nm vs 0.72 nm) are very close, and their oxides have good binding properties. Using zinc hydroxide as a support can improve the dispersion of copper in the preparation of the water-saving, energy-saving, and environmentally friendly copper-based catalyst of the present invention. Simultaneously, zinc oxide has a certain adsorption toxicity effect, resulting in good toxicity resistance and good impurity resistance during catalyst use.

[0011] According to some embodiments of the present invention, the silicon source includes silica sol or water glass (sodium silicate aqueous solution). These two inexpensive and readily available industrial raw materials are commonly used to prepare silica-supported metal catalysts, both of which contain silicon species, water, and a small amount of alkali metals. In the preparation of the water-saving, energy-saving, and environmentally friendly copper-based catalyst of the present invention, the silicon species and alkali metals in the silica sol and sodium silicate aqueous solution, especially the raw water, are fully utilized. In some embodiments, the catalyst can be prepared without adding additional water.

[0012] According to some embodiments of the present invention, the mass percentages of the copper hydroxide and the carrier are 4-70% and 30-96%, respectively, preferably 8.4-26.9% and 73.1-91.6%; for example, 16.7% and 83.3%; 22.4% and 77.6%; 26.9% and 73.1%; 14.8% and 85.2%; and 8.4% and 91.6%.

[0013] According to some embodiments of the present invention, a modifying agent is also added during the mixing process, wherein the mass percentages of the copper hydroxide, the carrier, and the modifying agent are 8.4–26.9%, 73.1–91.6%, and 0–12%, respectively, preferably 8.4–26.9%, 73.1–91.6%, and 0–12%; for example, 16.4%, 81.7%, and 1.9%.

[0014] According to some embodiments of the present invention, the modifying agent is selected from one or a combination of several of boehmite, sodium aluminate, sodium oxide and potassium oxide.

[0015] According to some embodiments of the present invention, the modifying agent is preferably boehmite or sodium aluminate.

[0016] According to some embodiments of the present invention, the mass percentage of alumina in the boehmite is 60-80%, preferably 65%.

[0017] According to some embodiments of the present invention, water is also added during the mixing process, wherein the mass percentages of the copper hydroxide, carrier, modifying agent and water are 8.4-26.9%, 30.8-91.6%, 0-12% and 0-50%, respectively; preferably 17.3%, 30.8%, 2.5% and 49.4%.

[0018] According to some embodiments of the present invention, the silicon source further includes at least one of silica and silicate ester; preferably, the silicon source further includes silica.

[0019] According to some embodiments of the present invention, the mass ratio of silica to silica sol is 0.02 to 0.07, preferably 0.07, or the mass ratio of silicate ester to silica sol is 0.10 to 0.25, preferably 0.23, or the mass ratio of silica to water glass is 0.05 to 0.2, preferably 0.1.

[0020] According to some embodiments of the present invention, the specific surface area of ​​silica is 145–300 m². 2 / g, preferably 200m 2 / g. High specific surface area (145~300m²) 2 The surface of the precipitated silica (g) has a large amount of Si-OH, which is weakly acidic. With the addition of modifying agents, the sodium and potassium ions contained therein can react with it to form Si-ONa or Si-OK, which neutralizes the acidity and can indirectly regulate the adsorption and desorption of cyclohexanol by the water-saving, energy-saving and environmentally friendly copper-based catalyst of this invention.

[0021] According to some embodiments of the present invention, a method for preparing a water-saving, energy-saving, and environmentally friendly copper-based catalyst includes the following steps:

[0022] First, the various raw material components are mixed into a fluid. After the fluid is thoroughly stirred, it is allowed to stand and dry. Then, the resulting solid is crushed, dried, granulated with additives, and finally pressed into tablets to obtain the water-saving, energy-saving, and environmentally friendly copper-based catalyst.

[0023] According to some embodiments of the present invention, the stirring temperature of the fluid is 25-90°C and the stirring time is 10-240 minutes; preferably, the stirring temperature is 40-60°C and the stirring time is 30-60 minutes; for example, the stirring temperature is 55°C and the stirring time is 90 minutes, or the stirring temperature is 50°C and the stirring time is 30 minutes, or the stirring temperature is 25°C and the stirring time is 60 minutes, or the stirring temperature is 30°C and the stirring time is 50 minutes, or the stirring temperature is 55°C and the stirring time is 30 minutes.

[0024] According to some embodiments of the present invention, the drying temperature is 100-250°C, preferably 200-220°C, for example 180°C, 100°C, 120°C, 220°C, 200°C, 150°C, 210°C or 160°C; the drying time is 8 hours to 48 hours, preferably 18-24 hours, for example 24 hours, 20 hours, 12 hours or 8 hours.

[0025] According to some embodiments of the present invention, the preparation method further includes passing the obtained water-saving, energy-saving and environmentally friendly copper-based catalyst through hydrogen gas for reduction treatment; preferably, the temperature of the reduction treatment is 180-230°C.

[0026] A second aspect of the present invention provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the above-described preparation method.

[0027] According to some embodiments of the present invention, the water-saving, energy-saving and environmentally friendly copper-based catalyst comprises copper oxide, zinc oxide and aluminum oxide; preferably, the mass percentages of copper oxide, zinc oxide and aluminum oxide are 10-60%, 20-70% and 1-20%, respectively.

[0028] According to some embodiments of the present invention, the mass percentages of copper oxide, zinc oxide and aluminum oxide in the water-saving, energy-saving and environmentally friendly copper-based catalyst are 34.5%, 61.6% and 3.9%, respectively.

[0029] According to some embodiments of the present invention, the water-saving, energy-saving and environmentally friendly copper-based catalyst comprises copper oxide and silicon dioxide; preferably, the water-saving, energy-saving and environmentally friendly copper-based catalyst comprises copper oxide with a mass percentage of 10-60%, silicon dioxide with a mass percentage of 40-90%, and aluminum oxide with a mass percentage of 0-5%.

[0030] According to some embodiments of the present invention, the mass percentages of copper oxide, silicon dioxide, aluminum oxide, and alkali metals in the water-saving, energy-saving, and environmentally friendly copper-based catalyst are 20.0–50.0%, 49.5–79.25%, and 0–3.1%, respectively; for example, 35.3%, 64.1%, 0; 35.3%, 53.1%, 0; 20.0%, 79.25%, 0; 50.0%, 49.5%, 0; 34.2%, 62.1%, 3.1%.

[0031] The third aspect of this invention provides the application of the above-mentioned water-saving, energy-saving, and environmentally friendly copper-based catalyst in the catalytic technology of organic hydrogenation and dehydrogenation.

[0032] Beneficial effects:

[0033] (1) The copper oxide in the water-saving, energy-saving and environmentally friendly copper-based catalyst obtained in this invention has a smaller particle size and higher low-temperature reducibility, thus the water-saving, energy-saving and environmentally friendly copper-based catalyst exhibits high catalytic activity in the cyclohexanol dehydrogenation model reaction.

[0034] (2) The raw materials for preparing the water-saving, energy-saving and environmentally friendly copper-based catalyst of the present invention do not include components such as carbonates and nitrates. The prepared water-saving, energy-saving and environmentally friendly copper-based catalyst contains almost no nitrogen or carbon substances. Therefore, the water-saving, energy-saving and environmentally friendly copper-based catalyst hardly releases nitrogen oxides, carbon monoxide or carbon dioxide during use. The toxic effect of the tail gas it produces on other supporting catalysts, especially precious metal catalysts, in large-scale equipment can be ignored.

[0035] (3) The preparation method of the water-saving, energy-saving and environmentally friendly copper-based catalyst of the present invention does not use precipitants (sodium carbonate, sodium bicarbonate, urea, etc.), does not introduce nitrogen and carbon components and does not require any form of washing treatment. The preparation method of the present invention only emits a small amount of water vapor and does not generate liquid wastewater. Therefore, the water consumption for preparing each gram of water-saving, energy-saving and environmentally friendly copper-based catalyst is less than 2 mL.

[0036] (4) The preparation of the water-saving, energy-saving and environmentally friendly copper-based catalyst of the present invention is carried out at a temperature below 250°C. It not only has low requirements for equipment, but also saves electricity and energy. Attached Figure Description

[0037] Figure 1 From top to bottom are the X-ray diffraction patterns of the water-saving, energy-saving, and environmentally friendly copper-based catalysts prepared in Examples 1-3 and Comparative Example 3;

[0038] Figure 2 TEM image of the water-saving, energy-saving, and environmentally friendly copper-based catalyst prepared in Example 1;

[0039] Figure 3 TEM image of the water-saving, energy-saving, and environmentally friendly copper-based catalyst prepared in Example 2;

[0040] Figure 4 TEM image of the water-saving, energy-saving, and environmentally friendly copper-based catalyst prepared in Example 3;

[0041] Figure 5 TEM image of the water-saving, energy-saving, and environmentally friendly copper-based catalyst prepared for Comparative Example 3. Detailed Implementation

[0042] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to these embodiments.

[0043] In this embodiment of the invention:

[0044] The alkaline sodium silica sol JN-25 was purchased from Qingdao Haiwan Fine Chemical Co., Ltd., batch number HY01101-825, with a silica content of 25 wt.% and a Na2O content of 0.3 wt.%.

[0045] Water glass (sodium silicate aqueous solution) was purchased from Tianjin Hengxing Chemical Reagent Manufacturing Co., Ltd., with a SiO2 content of 29 wt.% and a Na2O content of 8.5 wt.%.

[0046] Ethyl orthosilicate was purchased from Tianjin Kemei Chemical Reagent Co., Ltd., with a purity of 98 wt.%.

[0047] Example 1

[0048] This embodiment provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the following method:

[0049] The preparation of the water-saving, energy-saving, and environmentally friendly copper-based catalyst of this invention is carried out in an open reaction vessel. Specifically, under water bath conditions at 55°C, 420g of alkaline sodium silicate sol JN-25 (silica content 25wt.%) is added to a container equipped with a stirrer, followed by the addition of 89.8g of copper hydroxide, and finally 28g of silica (specific surface area 200m²). 2 The mixture was stirred continuously for 90 minutes until it became viscous, at which point stirring was stopped. The resulting mixture was then transferred to a tray and dried at 180°C for 24 hours. Finally, the dried solid was pulverized, dried, granulated with additives, and compressed into tablets to obtain a water-saving, energy-saving, and environmentally friendly copper-based catalyst. This catalyst contains 35.3 wt.% copper oxide, 64.1 wt.% silica, and 0.6 wt.% sodium oxide.

[0050] The X-ray diffraction pattern of the water-saving, energy-saving, and environmentally friendly copper-based catalyst prepared in Example 1 above is shown below. Figure 1 As shown, the TEM image is as follows Figure 2 As shown.

[0051] Example 2

[0052] This embodiment provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the following method:

[0053] Example 1 was repeated, but 283.4 g of sodium silicate aqueous solution (silica content 29 wt.%) was used instead of 420 g of alkaline sodium silicate sol JN-25 (silica content 25 wt.%) in Example 1. The stirring temperature and time were changed to stirring at a water bath temperature of 50°C for 30 minutes, and the drying temperature and time were changed to drying at a temperature of 150°C for 20 hours. In this water-saving, energy-saving, and environmentally friendly copper-based catalyst, the content of copper oxide is 35.3 wt.%, the content of silica is 53.1 wt.%, and the content of sodium oxide is 11.6 wt.

[0054] The X-ray diffraction pattern of the water-saving, energy-saving, and environmentally friendly copper-based catalyst prepared in Example 2 above is shown below. Figure 1 As shown, the TEM image is as follows Figure 3 As shown.

[0055] Example 3

[0056] This embodiment provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the following method:

[0057] Repeat Example 1, but replace the 28g of silica (specific surface area 200m²) in Example 1 with 97.2g of tetraethyl orthosilicate (silica content 28.8wt.%). 2 The stirring temperature and time were changed to 30 minutes at a water bath temperature of 50℃, and the drying temperature and time were changed to 20 hours at a temperature of 120℃. In this water-saving, energy-saving, and environmentally friendly copper-based catalyst, the content of copper oxide is 35.3 wt.%, the content of silicon dioxide is 64.1 wt.%, and the content of sodium oxide is 0.6 wt.%.

[0058] The X-ray diffraction pattern of the water-saving, energy-saving, and environmentally friendly copper-based catalyst prepared in Example 3 above is shown below. Figure 1 As shown, the TEM image is as follows Figure 4 As shown.

[0059] Example 4

[0060] This embodiment provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the following method:

[0061] Example 1 was repeated, but 41.2 g of copper hydroxide was used instead of the 89.8 g of copper hydroxide in Example 1, and the drying temperature and time were changed to 100°C for 24 hours. In this water-saving, energy-efficient, and environmentally friendly copper-based catalyst, the mass percentage of copper oxide is 20.0%, the content of silicon dioxide is 79.25 wt.%, and the content of sodium oxide is 0.75 wt.%.

[0062] Example 5

[0063] This embodiment provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the following method:

[0064] Example 1 was repeated, but 164.7 g of copper hydroxide was used instead of the 89.8 g of copper hydroxide in Example 1. The stirring time was changed to 30 minutes, and the drying temperature and time were changed to drying at 200°C for 24 hours. In this water-saving, energy-saving, and environmentally friendly copper-based catalyst, the content of copper oxide is 50.0 wt.%, the content of silicon dioxide is 49.5 wt.%, and the content of sodium oxide is 0.5 wt.%.

[0065] Example 6

[0066] This embodiment provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the following method:

[0067] Repeat Example 1, but after adding copper hydroxide, add an additional 10.26 g of pseudoboehmite (alumina content 65 wt.%); change the stirring temperature and time to stirring for 60 minutes at a water bath temperature of 25°C, and change the drying temperature and time to drying for 12 hours at a temperature of 220°C. In this water-saving, energy-saving, and environmentally friendly copper-based catalyst, the content of copper oxide is 34.2 wt.%, the content of alumina is 3.1 wt.%, the content of silica is 62.1 wt.%, and the content of sodium oxide is 0.6 wt.

[0068] Example 7

[0069] This embodiment provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the following method:

[0070] Example 6 was repeated, but 10.76 g of sodium aluminate (62 wt.% alumina content) was used instead of 10.26 g of boehmite (65 wt.% alumina content) in Example 4; the stirring temperature and time were changed to 50 minutes at a water bath temperature of 30°C, and the drying temperature and time were changed to 8 hours at a temperature of 210°C. In this catalyst, the content of copper oxide was 34.2 wt.%, the content of alumina was 3.1 wt.%, the content of silica was 62.1 wt.%, and the content of sodium oxide was 0.6 wt.

[0071] Example 8

[0072] This embodiment provides a water-saving, energy-saving, and environmentally friendly copper-based catalyst, which is prepared by the following method:

[0073] Under a water bath temperature of 55℃, 202g of deionized water was added to a container equipped with a stirrer, followed by 71g of copper hydroxide, and finally 126g of zinc hydroxide and 10.26g of boehmite (alumina content 65wt.%). The mixture was stirred continuously for 30 minutes until it became fine and homogeneous, at which point stirring was stopped. The resulting mixture was transferred to a tray and dried at 150℃ for 24 hours. The dried solid was then pulverized, dried, granulated with additives, and finally pressed into tablets to obtain a water-saving, energy-saving, and environmentally friendly copper-based catalyst. In this catalyst, the content of copper oxide was 34.5wt.%, the content of zinc oxide was 61.6wt.%, and the content of alumina was 3.9wt.

[0074] Comparative Example 1

[0075] This comparative example provides a copper-based catalyst, which is prepared by the following method:

[0076] Prepare a mixed solution a by mixing 1000 ml of 1.0 M copper nitrate solution and 50 ml of 1.0 M calcium nitrate solution. Co-precipitate the sodium carbonate solution with 958 g of silica sol JN-25 in a stirred precipitation tank, controlling the precipitation temperature at 60℃~70℃. The final pH value of the precipitation is 7.5. Then age the solution at 70℃~75℃ for 30 min. Add solution a to the precipitate, wash, dry, pulverize, calcine at 320℃, add appropriate amounts of water and graphite, and finally compress into tablets to obtain a usable catalyst. The copper content in this copper-based catalyst is 20.6 wt.%.

[0077] Comparative Example 2

[0078] This comparative example provides a copper-based catalyst, which is prepared by the following method:

[0079] Take 1000 ml of 1.0 M copper nitrate solution (solution a) and co-precipitate it with sodium carbonate solution and 637 g of silica sol JN-25 in a stirred precipitation tank. Control the precipitation temperature at 60℃~70℃, and the final pH value of precipitation is 7.5. Then age it at 70℃~75℃ for 30 min. Then add solution a to the above precipitate, wash, dry, crush, calcine at 320℃, add 13.0 g of sodium carbonate, appropriate amount of water and graphite, and finally compress into tablets to obtain the usable catalyst. The copper content in this copper-based catalyst is 27.9 wt.%.

[0080] The above Comparative Examples 1 and 2 refer to Examples 3 and 5 in the invention patent CN104511277A.

[0081] Comparative Example 3

[0082] This comparative example provides a copper-based catalyst, which is prepared by the following method:

[0083] Mix 1200 ml of 1.0 M copper nitrate solution, 2400 ml of 1.0 M zinc nitrate solution, and 100 ml of 3.0 M aluminum nitrate solution. While stirring, add the mixture dropwise to a 15% sodium carbonate solution at 30℃~80℃. Then, age the mixture at 60℃ for 30 minutes. After washing, filter, dry, and granulate, calcine at 400℃ for 2 hours. Finally, compress the granules to obtain a usable copper-based catalyst. The copper-based catalyst contains 27.6 wt.% copper oxide, 62.3 wt.% zinc oxide, and 10.1 wt.% aluminum oxide.

[0084] The X-ray diffraction pattern of the copper-based catalyst prepared in Comparative Example 3 is shown below. Figure 1 As shown, the TEM image is as follows Figure 5 As shown.

[0085] Experimental Example

[0086] To further illustrate the advancements of this invention, the water-saving, energy-saving, and environmentally friendly copper-based catalyst samples prepared in Examples 1-8 and the copper-based catalyst samples prepared in Comparative Examples 1-3 were subjected to reduction treatment with a mixture of hydrogen and nitrogen gas before the dehydrogenation reaction. The reduction treatment was carried out at a temperature of 180-230°C for 180 hours, with a hydrogen volume concentration of 80% in the mixture. Activity was evaluated in a ￠32×2mm fixed-bed reactor, specifically with a cyclohexanol space velocity of 0.60 h⁻¹. -1 The activity was evaluated under the conditions of controlling the reaction temperature at 230℃ and the catalyst loading at 50ml. The results are shown in Table 1 below.

[0087] Table 1

[0088]

[0089]

[0090] *Total water consumption = Raw material moisture content + Washing water consumption.

[0091] As can be seen from the experimental results in Table 1 above, the water-saving, energy-saving, and environmentally friendly copper-based catalysts prepared by the methods of Examples 1-7 of this invention use silicon as a support, while the water-saving, energy-saving, and environmentally friendly copper-based catalysts prepared by the method of Example 8 use zinc hydroxide as a support. The water-saving, energy-saving, and environmentally friendly copper-based catalyst samples prepared in Examples 1-8 exhibit higher cyclohexanol conversion and cyclohexanone selectivity during activity evaluation. Furthermore, in the preparation of the water-saving, energy-saving, and environmentally friendly copper-based catalysts in Examples 1-7 of this invention, only the water contained in the alkaline sodium silicate sol JN-25 or sodium silicate aqueous solution was used. In the preparation of the water-saving, energy-saving, and environmentally friendly copper-based catalyst in Example 8, 202g of deionized water was added, compared to comparative examples 1-3. Without adding a precipitant, the prepared water-saving, energy-saving, and environmentally friendly copper-based catalyst does not require washing, which can significantly reduce the water consumption during the preparation of copper-based catalysts, thus achieving a water-saving effect. Furthermore, the entire preparation process of the water-saving, energy-saving, and environmentally friendly copper-based catalyst of this invention is carried out at a temperature below 250°C, which can significantly reduce energy consumption, achieving an energy-saving effect and facilitating the production of smaller nano-copper particles. Finally, the water-saving, energy-saving, and environmentally friendly copper-based catalyst prepared by the method of this invention does not contain nitrogen, carbon, or other components. During use, the water-saving, energy-saving, and environmentally friendly copper-based catalyst releases almost no nitrogen oxides, carbon monoxide, or carbon dioxide, and the toxic effects of its exhaust gas on other supporting catalysts, especially precious metal catalysts, in large-scale equipment are negligible.

[0092] Furthermore, from the present invention Figure 1 It can be seen that in the water-saving, energy-saving and environmentally friendly copper-based catalysts prepared by the preparation method proposed in Examples 1-3 and the copper-based catalysts prepared by the existing preparation method in Comparative Example 3, copper exists in the form of copper oxide.

[0093] from Figures 2-5 As shown, the average particle size of copper oxide in the water-saving, energy-saving, and environmentally friendly copper-based catalysts prepared in Examples 1-3 is smaller than that in the copper-based catalyst prepared in Comparative Example 3. This is mainly attributed to the fact that the preparation operations of the water-saving, energy-saving, and environmentally friendly copper-based catalysts provided in Examples 1-3 of this invention are all carried out at relatively low temperatures (120-180°C). Therefore, the copper-based catalyst preparation method of this invention not only has low requirements for production equipment but also saves energy.

[0094] 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 water, energy and environment saving copper-based catalyst, characterized in that, The preparation method comprises the following steps: mixing copper hydroxide and a carrier, and then drying to obtain the water-saving, energy-saving and environment-friendly copper-based catalyst. The carrier comprises a silicon source, and the drying temperature is 100-250 DEG C.

2. The method for preparing a water, energy and environment friendly copper-based catalyst according to claim 1, characterized in that, The silicon source comprises silica sol or water glass. The mass percentage of the copper hydroxide and the carrier is 4-70% and 30-96% respectively.

3. The method for preparing a water, energy and environment friendly copper-based catalyst according to claim 2, characterized in that, The mass percentage of the copper hydroxide and the carrier is 8.4-26.9% and 73.1-91.6% respectively.

4. The method for preparing a water, energy and environment friendly copper-based catalyst according to any one of claims 1-3, characterized in that, A modifying agent is added during the mixing process.

5. The method for preparing the water, energy and environment friendly copper-based catalyst according to claim 4, characterized in that, The mass percentage of the copper hydroxide, the carrier and the modifying agent is 8.4-26.9%, 73.1-91.6% and 0-12% respectively. The modifying agent is at least one selected from pseudo-boehmite, sodium aluminate, sodium oxide and potassium oxide.

6. The method for preparing a water, energy and environment friendly copper-based catalyst according to claim 5, characterized in that, The mass percentage of the copper hydroxide, the carrier and the modifying agent is 8.4-26.9%, 73.1-91.6% and 0-1.9% respectively. The modifying agent is pseudo-boehmite or sodium aluminate.

7. The method for preparing the water, energy and environment friendly copper-based catalyst according to claim 6, characterized in that, The mass percentage of aluminum oxide in the pseudo-boehmite is 60-80%.

8. The method for preparing the water, energy and environment friendly copper-based catalyst according to claim 7, characterized in that, The mass percentage of aluminum oxide in the pseudo-boehmite is 65%.

9. The method for preparing water, energy and environment friendly copper-based catalyst according to any one of claims 1-3, characterized in that, Water is added during the mixing process.

10. The method for preparing the water, energy and environment friendly copper-based catalyst according to claim 9, characterized in that, The mass percentage of the copper hydroxide, the carrier, the modifying agent and water is 8.4-26.9%, 30.8-91.6%, 0-12% and 0-50% respectively.

11. The method for preparing the water, energy and environment friendly copper-based catalyst according to claim 10, characterized in that, The mass percentage of the copper hydroxide, the carrier, the modifying agent and water is 17.3%, 30.8%, 2.5% and 49.4% respectively.

12. The method for preparing a water, energy and environment friendly copper-based catalyst according to any one of claims 1-3, characterized in that, The silicon source further comprises at least one of white carbon black and silicate.

13. The method for preparing the water, energy and environment friendly copper-based catalyst according to claim 12, characterized in that, The silicon source further comprises white carbon black.

14. The method for preparing a water, energy and environment friendly copper-based catalyst according to claim 12, characterized in that, The mass ratio of the white carbon black to the silica sol is 0.02-0.07, or the mass ratio of the silicate to the silica sol is 0.10-0.25, or the mass ratio of the white carbon black to the water glass is 0.05-0.

2.

15. The method for preparing the water, energy and environment friendly copper-based catalyst according to claim 14, characterized in that, The mass ratio of the white carbon black to the silica sol is 0.07, or the mass ratio of the silicate to the silica sol is 0.23, or the mass ratio of the white carbon black to the water glass is 0.

1.

16. The method for preparing a water, energy and environment friendly copper-based catalyst according to claim 12, characterized in that, The specific surface area of the white carbon black is 145-300 m 2 / g.

17. The method for preparing the water, energy and environment friendly copper-based catalyst according to claim 16, characterized in that, The specific surface area of the white carbon black is 200 m 2 / g.

18. The method for preparing the water, energy and environment friendly copper-based catalyst according to any one of claims 1-3, characterized in that, The preparation method comprises the following steps: The various raw material components are first mixed into a fluid, and then the fluid is stirred and dried; then the obtained solid after drying is crushed, dried, granulated by adding an agent, and finally tabletted to obtain the water-saving, energy-saving and environment-friendly copper-based catalyst.

19. The method of claim 18, wherein, The stirring temperature of the fluid is 25-90 DEG C, and the stirring time is 10-240 minutes; The drying temperature is 100-250 DEG C, and the drying time is 8-48 hours; The preparation method further comprises reducing treatment of the obtained water-saving, energy-saving and environment-friendly copper-based catalyst by passing hydrogen.

20. The method of claim 19, wherein, The stirring temperature is 40-60 DEG C, and the stirring time is 30-60 minutes; The drying temperature is 200-220 DEG C, and the drying time is 18-24 hours; The reducing treatment temperature is 180-230 DEG C. 21.A water-saving, energy-saving and environment-friendly copper-based catalyst prepared by the preparation method in any one of claims 1-20.

22. The water, energy and environment friendly copper-based catalyst according to claim 21, characterized in that, The water-saving, energy-saving and environment-friendly copper-based catalyst comprises copper oxide, zinc oxide and aluminum oxide. Alternatively, the water-saving, energy-saving and environment-friendly copper-based catalyst comprises copper oxide and silicon dioxide.

23. The water, energy and environment friendly copper-based catalyst according to claim 22, characterized in that, The mass percentage of the copper oxide, zinc oxide and aluminum oxide is 10-60%, 20-70% and 1-20%, respectively; more preferably, the mass percentage of the copper oxide, zinc oxide and aluminum oxide is 34.5%, 61.6% and 3.9%, respectively. Alternatively, the water-saving, energy-saving and environment-friendly copper-based catalyst comprises copper oxide, silicon dioxide and aluminum oxide with mass percentage of 10-60%, 40-90% and 0-5%, respectively.

24. The water, energy and environment friendly copper-based catalyst according to claim 23, characterized in that, The mass percentage of the copper oxide, zinc oxide and aluminum oxide is 34.5%, 61.6% and 3.9%, respectively. Alternatively, the water-saving, energy-saving and environment-friendly copper-based catalyst comprises copper oxide, silicon dioxide and aluminum oxide with mass percentage of 20-50%, 49.5-79.25% and 0-3.1%, respectively.

25. Application of the water-saving, energy-saving and environment-friendly copper-based catalyst prepared by the preparation method of any one of claims 1-20 or the water-saving, energy-saving and environment-friendly copper-based catalyst of any one of claims 21-24 in organic matter hydrogenation and dehydrogenation catalysis technology.

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