阅读说明：本技术 层状硅酸铜复合物的制备方法 (Preparation method of layered copper silicate compound ) 是由 赵悦 陈世安 任海波 具月仙 张立忠 施岩 孟祥祺 于 2018-08-08 设计创作，主要内容包括：本发明提供了一种层状硅酸铜复合物的制备方法。该制备方法包括以下步骤：S1,将铜盐和含氨溶液混合,得到铜铵络合物溶液；S2,将铜铵络合物溶液与可溶性无机硅溶液混合,得到混合溶液；S3,将混合溶液脱氨；该制备方法还包括以下步骤：将结构支撑剂加入铜铵络合物溶液或混合溶液中,在步骤S3中的脱氨的过程中或脱氨的过程之后进行支撑反应,得到层状硅酸铜复合物；或在步骤S3中得到层状硅酸铜,在步骤S3之后将结构支撑剂加入层状硅酸铜中进行支撑反应,得到层状硅酸铜复合物。本发明的产品拥有比传统制备方法制备的产品更大的比表面积、孔径及孔容,发明工艺简单,脱除的氨气可收集并循环使用,成本降低,对环境友好。(The invention provides a preparation method of a layered copper silicate composite. The preparation method comprises the following steps: s1, mixing the copper salt and the ammonia-containing solution to obtain a copper-ammonium complex solution; s2, mixing the copper-ammonium complex solution with the soluble inorganic silicon solution to obtain a mixed solution; s3, deaminating the mixed solution; the preparation method also comprises the following steps: adding a structural propping agent into the copper ammonium complex solution or the mixed solution, and carrying out a propping reaction in or after the deamination process in the step S3 to obtain a layered copper silicate compound; or obtaining the layered copper silicate in step S3, and adding a structural proppant to the layered copper silicate after step S3 to perform a propping reaction to obtain a layered copper silicate composite. The product of the invention has larger specific surface area, aperture and pore volume than the product prepared by the traditional preparation method, the invention has simple process, the removed ammonia gas can be collected and recycled, the cost is reduced, and the invention is environment-friendly.)

1. A method for preparing a layered copper silicate composite, comprising the steps of:

s1, mixing the copper salt and the ammonia-containing solution to obtain a copper-ammonium complex solution;

s2, mixing the copper ammonium complex solution with a soluble inorganic silicon solution to obtain a mixed solution;

s3, deaminating the mixed solution;

the preparation method also comprises the following steps:

adding a structural propping agent into the copper ammonium complex solution or the mixed solution, and carrying out a propping reaction during or after the deamination in the step S3 to obtain the layered copper silicate composite; or

Obtaining copper phyllosilicate in the step S3, and adding a structural propping agent into the copper phyllosilicate to perform a propping reaction after the step S3 to obtain the copper phyllosilicate composite.

2. The method of claim 1, wherein the copper salt comprises any one or more of copper nitrate, copper sulfate, copper chloride, copper acetate, and copper carbonate, and preferably the ammonia-containing solution comprises any one or more of ammonia, methylamine, and dimethylamine.

3. The method according to claim 1 or 2, wherein in step S1, the copper ion concentration in the copper-ammonium complex solution is 0.05 to 0.2mol/L, and the molar ratio of copper to ammonia is 1 to 3: 1.

4. The method of claim 1, wherein the soluble inorganic silicon solution comprises any one or more of a silica sol solution, a sodium silicate solution, and potassium silicate.

5. The method according to claim 1 or 4, wherein in step S2, the molar ratio of copper to silicon in the mixed solution is 6-8: 1.

6. The method according to claim 1, wherein between the step S2 and the step S3, the method further comprises a step of aging the mixed solution, preferably stirring the mixed solution, so as to age the mixed solution, preferably for 4 to 12 hours.

7. The production method according to claim 1, wherein, when the supporting reaction is carried out by adding the structural proppant to the copper phyllosilicate,

carrying out the support reaction by adopting a solid phase support method, preferably, the solid phase support method is mechanical stirring or grinding treatment; or

Adding the layered copper silicate into a solvent to obtain a copper silicate solution, and then adding the structural propping agent into the copper silicate solution by adopting a liquid phase supporting method to carry out the supporting reaction, wherein the liquid phase supporting method is preferably mechanical stirring, ultrasonic treatment or microwave treatment; or

Adding the heat-treated layered copper silicate into a solvent to obtain a copper silicate solution, and then adding the structural propping agent into the copper silicate solution by adopting a liquid phase supporting method to carry out the supporting reaction, wherein the heat treatment preferably comprises drying and roasting, and the liquid phase supporting method is preferably mechanical stirring, ultrasonic treatment or microwave treatment.

8. The method for preparing a composite material according to claim 7, wherein the step S3 includes the steps of:

s31, heating the mixed solution, wherein the preferable heating temperature is 70-100 ℃;

s32, performing ammonia evaporation or gas stripping on the mixed solution to remove ammonia from the mixed solution to obtain a deamination solution, wherein the pH value of the deamination solution is preferably 5-7;

s33, filtering the deamination solution to obtain a filtrate and the copper phyllosilicate, wherein the specific surface area of the copper phyllosilicate is preferably 500-550 m²/g。

9. The method for preparing a copper-ammonium complex catalyst according to claim 1, wherein the step S3 comprises the steps of, when the structural proppant is added to the copper-ammonium complex solution or the mixed solution to perform the supporting reaction:

s31, heating the mixture of the mixed solution and the structural propping agent, wherein the preferable heating temperature is 70-100 ℃;

s32, performing ammonia evaporation or gas stripping on the mixed solution to remove ammonia from the mixed solution, and performing the supporting reaction in or after the deamination process to obtain a deamination solution, wherein the pH value of the deamination solution is preferably 5-7, and the supporting reaction is preferably performed by mechanical stirring, ultrasonic treatment or microwave treatment;

s33, filtering the deamination solution to obtain a filtrate and the copper phyllosilicate compound.

10. The production method according to claim 8 or 9, wherein, after the step S33, the step S3 further includes the steps of:

collecting the ammonia gas, preferably collecting the ammonia gas by using deionized water or the filtrate.

11. The method according to claim 1, wherein the temperature of the support reaction is 20 to 500 ℃ and the pressure of the support reaction is 0.05 to 2.0 MPa.

12. The method of claim 1, wherein the structural proppant comprises any one or more of potassium acetate, potassium propionate, sodium acrylate, rubidium chloride, cesium bromide amino acids, pyridine, methanol, acetonitrile, hexamethylene diamine, benzamide, acrylamide, ammonium acetate, cyclic imines, p-nitroaniline, and fatty acid salts.

13. The method of claim 1, wherein after the copper phyllosilicate composite is obtained, the method further comprises the step of heat treating the copper phyllosilicate composite, preferably wherein the heat treating comprises drying and firing.

Technical Field

The invention relates to the field of catalyst preparation, in particular to a preparation method of a layered copper silicate compound.

Background

The layered silicate is a special silicate with an obvious sheet structure, the layered silicate is mainly formed in catalysts such as silicon dioxide loaded copper, nickel-cobalt-zinc and the like, wherein the silicon dioxide loaded copper-based catalyst is widely applied to the reaction of preparing ethylene glycol and ethanol by hydrogenating oxalate with excellent catalytic performance, and copper atoms of the layered copper silicate are combined with a carrier through Si-O-Cu bonds, so that the copper atoms are easily reduced into Cu in the reduction process⁺. The study showed that. Cu + plays an important role in oxalate hydrogenation. In addition, the larger specific surface area of copper silicate is more beneficial to improving the dispersion reaction activity of copper species.

Disclosure of Invention

The invention mainly aims to provide a preparation method of a layered copper silicate composite, so that the layered copper silicate composite can have a large specific surface area.

In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a layered copper silicate composite, comprising the steps of: s1, mixing the copper salt and the ammonia-containing solution to obtain a copper-ammonium complex solution; s2, mixing the copper-ammonium complex solution with the soluble inorganic silicon solution to obtain a mixed solution; s3, deaminating the mixed solution; the preparation method also comprises the following steps: adding a structural propping agent into the copper ammonium complex solution or the mixed solution, and carrying out a propping reaction in or after the deamination process in the step S3 to obtain a layered copper silicate compound; or obtaining the layered copper silicate in step S3, and adding a structural proppant to the layered copper silicate after step S3 to perform a propping reaction to obtain a layered copper silicate composite.

Further, the copper salt includes any one or more of copper nitrate, copper sulfate, copper chloride, copper acetate and copper carbonate, and preferably the ammonia-containing solution includes any one or more of ammonia water, methylamine and dimethylamine.

Further, in step S1, the copper ion concentration in the cuprammonium complex solution is 0.05-0.2 mol/L, and the cuprammonium molar ratio is 1-3: 1.

Further, the soluble inorganic silicon solution includes any one or more of a silica sol solution, a sodium silicate solution, and potassium silicate.

Further, in step S2, the molar ratio of copper to silicon in the mixed solution is 6-8: 1.

Further, between the step S2 and the step S3, the preparation method further comprises the step of aging the mixed solution, preferably stirring the mixed solution to age the mixed solution, preferably the aging time is 4-12 h.

Further, when the structural propping agent is added into the layered copper silicate for carrying out the supporting reaction, a solid phase supporting method is adopted for carrying out the supporting reaction, and the solid phase supporting method is preferably mechanical stirring or grinding treatment; or adding the layered copper silicate into a solvent to obtain a copper silicate solution, and then adding a structural propping agent into the copper silicate solution by adopting a liquid phase supporting method for supporting reaction, wherein the liquid phase supporting method is preferably mechanical stirring, ultrasonic treatment or microwave treatment; or adding the heat-treated layered copper silicate into a solvent to obtain a copper silicate solution, and then adding a structural propping agent into the copper silicate solution by adopting a liquid phase support method for carrying out a support reaction, wherein the heat treatment preferably comprises drying and roasting, and the liquid phase support method is preferably mechanical stirring, ultrasonic treatment or microwave treatment.

Further, step S3 includes the steps of: s31, heating the mixed solution, wherein the preferable heating temperature is 70-100 ℃; s32, performing ammonia evaporation or gas stripping on the mixed solution to remove ammonia from the mixed solution to obtain a deamination solution, wherein the pH value of the deamination solution is preferably 5-7; s33, filtering the deamination solution to obtain filtrate and layered copper silicate, wherein the specific surface area of the layered copper silicate is preferably 500-550 m²/g。

Further, when the structural proppant is added to the cuprammonium complex solution or the mixed solution to perform the supporting reaction, the step S3 includes the following steps: s31, heating the mixture of the mixed solution and the structural propping agent, wherein the preferable heating temperature is 70-100 ℃; s32, performing ammonia evaporation or gas stripping on the mixed solution to remove ammonia from the mixed solution, and performing a supporting reaction in or after the deamination process to obtain a deamination solution, wherein the pH value of the deamination solution is preferably 5-7, and the supporting reaction is preferably performed by mechanical stirring, ultrasonic treatment or microwave treatment; s33, filtering the deamination solution to obtain a filtrate and a layered copper silicate composite.

Further, after the step S33, the step S3 further includes the steps of: collecting ammonia gas, preferably using deionized water or filtrate.

Furthermore, the temperature of the supporting reaction is 20-500 ℃, and the pressure of the supporting reaction is 0.05-2.0 MPa.

Further, the structural proppant comprises any one or more of potassium acetate, potassium propionate, sodium acrylate, rubidium chloride, cesium bromide amino acids, pyridine, methanol, acetonitrile, hexamethylene diamine, benzamide, acrylamide, ammonium acetate, cyclic imines, p-nitroaniline, and fatty acid salts.

Further, after obtaining the copper phyllosilicate composite, the preparation method further comprises the step of heat-treating the copper phyllosilicate composite, preferably the heat treatment comprises drying and baking.

The technical scheme of the invention is applied to provide a preparation method of a layered copper silicate compound, the method firstly utilizes ammonia water and copper salt to generate a copper ammonium complex, then inorganic silicon is added into the solution, copper silicate precipitate with a layered structure as a microstructure is obtained after ammonia gas is removed, meanwhile, a structural propping agent is inserted into the interlayer of the copper silicate by utilizing a propping reaction in the process to obtain the copper silicate compound, and the interlayer spacing of the copper silicate is increased due to the action of a macromolecular space structure of the propping agent, so that the function of modulating the interlayer spacing is realized, and the specific surface area is increased therewith. The product of the invention has larger specific surface area, aperture and pore volume than the product prepared by the traditional preparation method, the invention has simple process, the removed ammonia gas can be collected and recycled, the cost is reduced, and the invention is environment-friendly. The high specific surface area copper silicate of the invention can be used asCatalyst and carrier for preparing fatty alcohol and CO by hydrogenating fatty acid ester₂Catalytic hydrogenation to produce alcohol.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:

figure 1 shows a comparison of the XRD patterns of the products of example 1 and comparative example 1; and

figure 2 shows the pore size distribution plots for the products of example 1 and comparative example 1.

Detailed Description

It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.

In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged under appropriate circumstances in order to facilitate the description of the embodiments of the invention herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.

As described in the background art, the prior art has been effective in improving the activity of a catalyst by increasing the specific surface area of a carrier, increasing the uniform distribution of copper species on the carrier, and increasing the contact area with a reactant. In order to enable the layered copper silicate composite to have a large specific surface area, the invention provides a preparation method of the layered copper silicate composite, which comprises the following steps: s1, mixing the copper salt and the ammonia-containing solution to obtain a copper-ammonium complex solution; s2, mixing the copper-ammonium complex solution with the soluble inorganic silicon solution to obtain a mixed solution; s3, deaminating the mixed solution; the preparation method also comprises the following steps: adding a structural propping agent into the copper ammonium complex solution or the mixed solution, and carrying out a propping reaction in the deamination process or after the deamination process of step S3 to obtain a layered copper silicate compound; or obtaining the layered copper silicate in step S3, and adding a structural proppant to the layered copper silicate after step S3 to perform a propping reaction to obtain a layered copper silicate composite.

The preparation method of the layered copper silicate compound provided by the invention is adopted, firstly, the ammonia water and the copper salt are utilized to generate the copper-ammonium complex, then the inorganic silicon is added into the solution, the copper silicate precipitate with the microstructure of the layered structure is obtained after the ammonia gas is removed, meanwhile, the structural propping agent is inserted into the interlayer of the copper silicate by utilizing the supporting reaction in the process to obtain the copper silicate compound, and the interlayer spacing of the copper silicate is increased due to the action of the macromolecular space structure of the propping agent, so that the function of modulating the interlayer spacing is realized, and the specific surface area is increased accordingly. The product of the invention has larger specific surface area, aperture and pore volume than the product prepared by the traditional preparation method, the invention has simple process, the removed ammonia gas can be collected and recycled, the cost is reduced, and the invention is environment-friendly. The copper silicate with high specific surface area can be used as a catalyst and a carrier and applied to preparation of corresponding fatty alcohol and CO by hydrogenation of fatty acid ester₂Catalytic hydrogenation to produce alcohol.

An exemplary embodiment of a method for preparing a copper phyllosilicate composite provided in accordance with the present invention will be described in more detail below. These exemplary embodiments may, however, be embodied in many different forms and should not be construed as limited to only the embodiments set forth herein. It should be understood that these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of these exemplary embodiments to those skilled in the art.

First, step S1 is executed: and mixing the copper salt and the ammonia-containing solution to obtain a copper-ammonium complex solution. The copper salt may include any one or more of copper nitrate, copper sulfate, copper chloride, copper acetate and copper carbonate; the ammonia-containing solution may include any one or more of ammonia, methylamine and dimethylamine, but is not limited to the above-mentioned species, and those skilled in the art can reasonably select the species of the copper compound and the ammonia-containing solution according to the prior art.

In step S1, in order to improve the efficiency of the reaction to obtain the cuprammonium complex, the concentration of the copper ions in the cuprammonium complex solution is preferably 0.05 to 0.2mol/L, and the molar ratio of cuprammonium is preferably 1 to 3: 1.

After the above step S1, step S2 is executed: and mixing the copper ammonium complex solution with the soluble inorganic silicon solution to obtain a mixed solution. The soluble inorganic silicon solution may include any one or more of a silica sol solution, a sodium silicate solution, and potassium silicate, but is not limited to the above-mentioned species, and those skilled in the art can reasonably select the species of the soluble inorganic silicon solution according to the prior art.

In step S2, in order to improve the efficiency of the copper silicate obtained by the reaction after the deamination of the mixed solution, the molar ratio of copper to silicon in the mixed solution is preferably 6-8: 1.

After the step S2, the preparation method of the present invention may further include a step of aging the mixed solution, and in order to enhance the aging effect, it is more preferable that the mixed solution is stirred to age the mixed solution; more preferably, the aging time is 4 to 12 hours.

After the above step S2, step S3 is executed: and deaminating the mixed solution.

In a preferred embodiment, the copper phyllosilicate is obtained in the step S3, and after the step S3, the above preparation method of the present invention further includes the steps of: adding the structural propping agent into the layered copper silicate to carry out a propping reaction to obtain a layered copper silicate compound.

In order to obtain the above copper phyllosilicate, the above step S3 may include the steps of: s31, heating the mixed solution; s32, performing ammonia evaporation or gas stripping on the mixed solution to remove ammonia from the mixed solution to obtain a deamination solution; s33, filtering the deamination solution to obtain filtrate and layered copper silicate.

In order to improve the deamination efficiency, preferably, the mixed solution is heated to 70-100 ℃; in order to obtain a higher specific surface area, the pH value of the deamination solution is preferably 5 to 7. With the adoption of the preferable process conditions, after the deamination and filtration processes, the specific surface area of the layered copper silicate can reach 500-550 m²/g。

In the above step of adding the structural proppant to the copper phyllosilicate, a supporting reaction may be performed by a solid phase support method; in order to improve the supporting efficiency, the solid phase supporting method is preferably a mechanical stirring or grinding treatment. Or adding the layered copper silicate into a solvent to obtain a copper silicate solution, then adding a structural propping agent into the copper silicate solution by adopting a liquid phase supporting method to carry out a supporting reaction, or adding the heat-treated layered copper silicate into the solvent to obtain the copper silicate solution, then adding the structural propping agent into the copper silicate solution by adopting the liquid phase supporting method to carry out the supporting reaction, wherein the heat treatment can comprise drying and roasting; in order to improve the supporting efficiency, the above liquid phase supporting method is preferably mechanical stirring, ultrasonic treatment or microwave treatment.

In another preferred embodiment, the structural proppant is added to the copper ammonium complex solution or the mixed solution, and the above preparation method of the present invention further comprises the steps of: the supporting reaction is performed during or after the deamination in step S3 to obtain the copper phyllosilicate composite.

At this time, the above step S3 may include the steps of: s31, heating the mixture of the mixed solution and the structural propping agent; s32, performing ammonia evaporation or gas stripping on the mixed solution to remove ammonia from the mixed solution, and performing a supporting reaction in or after the deamination process to obtain a deamination solution; s33, filtering the deamination solution to obtain a filtrate and a layered copper silicate composite.

In order to improve the deamination efficiency, preferably, the mixture of the mixed solution and the structural propping agent is heated to 70-100 ℃; in order to obtain a higher specific surface area, the pH value of the deamination solution is preferably 5-7; also, in order to improve the supporting efficiency, it is preferable to perform the supporting reaction using mechanical stirring, ultrasonic treatment, or microwave treatment.

After the step S33 of obtaining filtrate, preferably, the step S3 further includes the steps of: collecting ammonia gas, preferably using deionized water or filtrate. Absorbing the ammonia released by heating, and recycling. And ammonia gas discharged in the deamination process in the step S32 is collected and recycled, so that the cost is reduced and the method is environment-friendly.

In order to improve the supporting efficiency, preferably, the temperature of the supporting reaction is 20-500 ℃, and the supporting reaction pressure is 0.05-2.0 MPa; also, preferably, the above-mentioned structural proppant includes any one or more of potassium acetate, potassium propionate, sodium acrylate, rubidium chloride, cesium bromide, amino acids, pyridine, methanol, acetonitrile, hexanediamine, benzamide, acrylamide, ammonium acetate, cyclic imine, p-nitroaniline, and fatty acid salts.

After the above step S3, the above preparation method of the present invention may further include a step of heat-treating the copper phyllosilicate composite, and the above heat treatment may include drying and firing. The layered copper silicate composite obtained after filtration or support is dried and calcined to achieve the desired structure of the catalyst.

The present invention is described in further detail below with reference to specific examples and comparative examples, which are not to be construed as limiting the scope of the invention as claimed.