CN113145142B - Preparation method of tin-based catalyst and application of tin-based catalyst in acetylene hydration reaction - Google Patents

Preparation method of tin-based catalyst and application of tin-based catalyst in acetylene hydration reaction Download PDF

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CN113145142B
CN113145142B CN202110179828.8A CN202110179828A CN113145142B CN 113145142 B CN113145142 B CN 113145142B CN 202110179828 A CN202110179828 A CN 202110179828A CN 113145142 B CN113145142 B CN 113145142B
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tin
based catalyst
acetylene
chloride
specific surface
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赵佳
岳玉学
庞祥雪
王柏林
朱文锐
王赛赛
冯涛
王涛
赵栋洋
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Zhejiang University of Technology ZJUT
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    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract

The invention discloses a preparation method of a tin-based catalyst and application of the tin-based catalyst in acetylene hydration reaction. The preparation method of the tin-based catalyst comprises the following steps: dissolving a tin-containing precursor and a base metal additive in a solvent, stirring to uniformly mix the precursor and the base metal additive, dripping the mixed solution onto a porous solid carrier at the temperature of 20-30 ℃, carrying out isovolumetric impregnation under the action of an electrostatic field for 0.5-2 hours, and then drying at the temperature of 40-110 ℃ for 8-24 hours to obtain a tin-based catalyst; the base metal auxiliary agent is one or more of Bi, Ba, Fe, Mn, Zn, K, Ca and Ni. The invention provides the application of the tin-based catalyst prepared by the preparation method in the acetaldehyde generation through acetylene hydration reaction, and solves the problems of poor acetylene conversion rate and selectivity and poor stability in the acetaldehyde generation reaction through acetylene hydration reaction.

Description

Preparation method of tin-based catalyst and application of tin-based catalyst in acetylene hydration reaction
(I) technical field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a tin-based catalyst and application of the tin-based catalyst in acetylene hydration reaction.
(II) background of the invention
Acetaldehyde is an important organic chemical raw material and is used for producing secondary products of important basic organic synthesis, such as acetic acid, acetic anhydride, butyraldehyde, butanol, octanol, pentaerythritol, trichloroacetaldehyde and the like. The acetaldehyde produced in industry mainly comprises four methods, namely an ethylene oxidation method, an ethanol dehydrogenation method, a low-carbon alkane oxidation method and an acetylene hydration method. Among them, the ethylene oxidation method is the most important method for producing acetaldehyde for the sixties of this century, and has been developed rapidly in recent years. In the developed countries of petrochemical industry, the ethylene process largely replaces the acetylene process, and the main reasons are as follows: (1) the development of petrochemical industry has provided a cheaper raw material for ethylene than acetylene; (2) the mercury sulfate-sulfuric acid catalyst used for acetylene hydration is extremely toxic and harmful to the health of workers.
The acetylene hydration process also has advantages over the ethylene oxidation process in certain respects. The acetylene hydration reaction does not need noble metal palladium catalyst, oxygen generating equipment and special acid-resistant materials. The resource structure of 'rich coal, lean oil and less gas' in China and the breakthrough of the technology of preparing acetylene from coal further expand the acetylene capacity, so that the acetaldehyde produced by the acetylene hydration method becomes the characteristic advantage route of the acetaldehyde production industry in China again.
The early research of acetylene hydration reaction uses mercury salt and acid as catalysts, however, due to the toxicity of mercury, the requirement of strong acid condition, and the reduction of activity caused by the fact that mercury is easy to be reduced in the reaction process, the wide application of acetylene hydration reaction is limited, and in order to better develop the acetylene hydration production to meet the current national requirement for acetaldehyde, a non-mercury catalyst which can be suitable for industrial production must be researched to replace a highly toxic mercury-based catalyst.
The research of acetylene gas phase hydration reaction non-mercury catalysts in China mainly focuses on cadmium calcium phosphate and zinc oxide systems. Cadmium in a cadmium calcium phosphate system is extremely toxic, has poor strength and high consumption, and a large amount of high polymers are easily generated on the surface of the catalyst, so that the production is abnormal and the product cost is high. The zinc oxide system has the advantages of non-toxic catalyst, high production capacity, low water-gas ratio, simple process flow, less three wastes and the like, but has the defects of poor selectivity, low conversion rate and the like. In addition, both systems require high temperature conditions of 400 ℃ to exhibit catalytic performance. From the viewpoint of industrial production, there is a problem of excessive energy consumption.
Chem,2018,42,6507-6514, a series of zinc-copper bimetallic catalysts are prepared and used as catalysts for acetylene hydration reaction, and the influence of a copper additive on the performance of the zinc catalyst is studied in detail. The copper metal and the zinc ions have strong interaction, and the loss of the zinc ions in the reaction process is prevented, so that the catalytic activity of the bimetallic catalyst for preparing acetaldehyde by acetylene hydration is improved. At the reaction temperature of 260 ℃ and the space velocity of 90h-1Under the condition of (1), the conversion rate of acetylene in 10h of the Zn-10Cu/MCM catalyst is about 98%, but the selectivity to acetaldehyde is poor and is only about 50%.
The document CATALYSIS LETTERS,2018,11,3370-3377 investigated several organic compounds containing S as ligands for cu (i) catalyzed acetylene hydration under mercury-free conditions. The results show that the minimum selectivity to acetaldehyde increased significantly from 3.61 to 87.56% due to the addition of mercaptosuccinic acid, while C2H2The minimum conversion of (a) also increased from 14.45 to 34.92%. The possible reasons for the increased selectivity of acetaldehyde were investigated by density functional theory calculations. The results show that the addition of an organic compound containing S can increase the Cu complex and C2H2The coordination ability of (a). Despite the increased selectivity of the added ligand, there is a distance from the conversion to the industrialization
Patent CN108311174A reports a catalytic system for preparing acetaldehyde by acetylene liquid phase hydration, which comprises cuprous chloride, inorganic acid, sulfo-organic acid and solvent, and also comprises inorganic chloride or organic nitrogen-containing hydrochloride. The system replaces the traditional mercury catalyst, and reduces the harmful effects on the environment and human bodies caused by the use of the mercury catalyst. At 60 ℃, the space velocity is introduced for 50h-1Of acetylene, the bodyThe acetylene conversion was the highest, but only 40%.
In view of the above, although research on non-mercury catalysts for acetylene hydration reaction has been advanced, the catalysts have problems of low activity and poor stability. Therefore, it is very significant to invent a tin-based catalyst, and further to improve the activity and stability in the acetylene hydration reaction.
Disclosure of the invention
The first technical problem to be solved by the invention is to provide a preparation method of a tin-based catalyst.
The second technical problem to be solved by the invention is to provide the application of the tin-based catalyst in the acetylene hydration reaction, so as to solve the problems of poor acetylene conversion rate and poor stability in the reaction of generating acetaldehyde through the acetylene hydration reaction.
In order to solve the technical problems, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a tin-based catalyst, comprising the steps of:
dissolving a tin-containing precursor and a base metal additive in a solvent, stirring to uniformly mix the precursor and the base metal additive, dripping the mixed solution onto a porous solid carrier at the temperature of 20-30 ℃, carrying out isovolumetric impregnation under the action of an electrostatic field for 0.5-2 hours, and then drying at the temperature of 40-110 ℃ for 8-24 hours to obtain a tin-based catalyst; the base metal auxiliary agent is one or more of Bi, Ba, Fe, Mn, Zn, K, Ca and Ni.
Furthermore, in the tin-based catalyst, the tin loading (relative to the mass of the carrier) is 10-30 wt%; the loading capacity (relative to the mass of the carrier) of the base metal auxiliary agent is 0.1-2 wt%.
Further, the tin-containing precursor is one of tin dichloride, dioctyltin, tin tetrachloride, tributyltin acetate and triphenyltin.
Further, the base metal auxiliary agent is one or a mixture of bismuth chloride, barium chloride, ferric chloride, manganese chloride, zinc chloride, potassium chloride, calcium chloride, tin chloride and nickel chloride.
Further, the solvent is one or a mixture of deionized water, absolute ethyl alcohol, tetrahydrofuran, methanol, acetone, diethyl ether, cyclohexane, carbon tetrachloride and benzene.
Further, the action conditions of the electrostatic fields are as follows: the electric field intensity is 10-50 kv/cm, and the processing time is 0.5-2 h.
The porous solid carrier is selected from one of activated carbon, activated carbon fiber, carbon nano tube, graphene, silicon dioxide, aluminum oxide, titanium dioxide and molecular sieve. The activated carbon is preferably columnar carbon or spherical activated carbon, the particle size is 20-100 meshes, and the specific surface area is 500-1500 m2The pore volume is 0.25-1.5 mL/g. The activated carbon fiber is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 500-1600 m2The pore volume is 0.25-2.5 mL/g. The carbon nano tube is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface is 250-1600 m2The pore volume is 0.25-2.5 mL/g. The graphene is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 500-3000 m2The pore volume is 0.25-2.5 mL/g. The aluminum oxide is preferably gamma-Al2O3And processed into columnar or spherical shape with particle size of 10-100 meshes and specific surface area of 250-800 m2The pore volume is 0.1-1.5 mL/g. The silicon dioxide is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2The pore volume is 0.1-1.5 mL/g. The titanium dioxide is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2The pore volume is 0.1-1.0 mL/g. The molecular sieve is preferably ZSM-5, a beta molecular sieve, a gamma molecular sieve, a 5A molecular sieve, a 10X molecular sieve or a 13X molecular sieve, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2The pore volume is 0.1-1.8 mL/g.
Further, the porous solid support is subjected to plasma treatment.
Further, the plasma processing conditions are: the current is 1-5A, the voltage is 10-25V, and the treatment time is 0.5-2 h; the plasma treatment is carried out at N2Carried out under an atmosphere, N2The flow rate is 5-60 ml/min.
Further, the activated carbon fiber is doped with nitrogen or phosphorus, and the doping process is as follows: preparing a nitrogen-containing or phosphorus-containing precursor into an aqueous solution with the mass fraction of 10-15%, and then dipping the activated carbon fiber in the aqueous solution of the nitrogen-containing or phosphorus-containing precursor for 1-5 h at the temperature of 30-60 ℃.
Furthermore, the nitrogen-containing precursor is ammonium chloride, urea or ethylenediamine, and the phosphorus-containing precursor is phosphoric acid.
In a second aspect, the invention provides the use of a tin-based catalyst as described in the hydration reaction of acetylene to acetaldehyde.
The application specifically comprises the following steps: the tin-based catalyst is filled in a reactor, and feed gas H is introduced2O and C2H2The reaction temperature is 100-200 ℃, the reaction pressure is 0.01-2 MPa, and acetaldehyde is obtained through reaction.
Further, the volume space velocity of acetylene is 5-500 h-1。
Compared with the prior art, the invention has the following innovation points and technical advantages:
(1) the invention applies the electrostatic field technology to the preparation process of the catalyst, is beneficial to the high dispersion degree and effective anchoring of the active components of the catalyst on the surface of the carrier, reduces the agglomeration of the active components, exerts high activity and can keep stable in the long-time reaction process.
(2) The invention adopts plasma technology to treat the carrier, can increase the oxygen-containing groups on the surface of the carrier in a short time, and the oxygen-containing groups can act as active centers or act together with metal active components, thereby obviously improving the catalytic activity.
(3) The tin-based catalyst prepared by the invention gets rid of the traditional mercury-based catalyst, avoids the harm of mercury loss to the environment and human body, and has the advantages of high catalytic activity, good stability and low cost.
(4) According to the preparation method of the tin-based catalyst, when the carrier is the activated carbon fiber, the carrier is subjected to nitrogen or phosphorus doping pretreatment, so that the catalytic activity can be remarkably improved.
(5) The tin-based catalyst prepared by the invention is applied to the generation of acetaldehyde by the hydration reaction of acetylene, and has the advantages of high acetylene conversion rate, high acetaldehyde selectivity and good stability.
(IV) detailed description of the preferred embodiments
The present invention will be described with reference to specific examples. It should be noted that the examples are only intended to illustrate the invention further, but should not be construed as limiting the scope of the invention, which is in no way limited thereto. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
Example 1
Selecting columnar activated carbon as carrier, with particle diameter of 20 mesh and specific surface area of 1000m2The pore volume is 1 mL/g. At room temperature, at 5ml/min N2And performing plasma treatment under the atmosphere, wherein the current is 1A, the voltage is 10V, and the plasma is taken out for standby after treatment for 0.5 h.
21.89g of tin tetrachloride and 0.21g of ZnCl2Dissolving in 100mL of methanol, stirring to mix uniformly, dripping the mixture on 100g of activated carbon carrier treated by plasma at 20 ℃, performing action treatment for 0.5h under the condition of an electrostatic field with the strength of 10kv/cm, taking out the mixture from the electrostatic field, and drying for 8h at 70 ℃ to obtain the tin-based catalyst, wherein the tin loading capacity is 10 percent, and ZnCl is used as a catalyst2The loading was 0.1%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the pressure is 0.1MPa, and the volume space velocity of acetylene is 300h-1After 2000h of reaction, the acetylene conversion was 99.30% and the acetaldehyde selectivity was 98.12%.
Example 2
Active carbon fiber is selected as a carrier, the particle size of the carrier is 100 meshes, and the specific surface area is 800m2The pore volume is 0.25 mL/g. At room temperature, at 10ml/min N2Performing plasma treatment under the atmosphere, performing current of 2A and voltage of 15V, taking out after 1h of treatment, then soaking the activated carbon fiber in ammonium chloride aqueous solution with mass fraction of 10% at 30 ℃, taking out after 5h of soaking, and drying for later use.
47.80g of tin dichloride and 2.25g of BiCl3Dissolving in 100mL deionized water, stirring to mix uniformly, dripping the mixture on 100g of activated carbon fiber carrier treated by plasma at 25 ℃, performing action treatment for 1.5h under the condition of an electrostatic field with the strength of 20kv/cm, taking out from the electrostatic field, and drying for 10h at 110 ℃ to obtain the tin-based catalyst, wherein the tin loading capacity is 30 percent, and the BiCl is3The loading was 2%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 110 ℃, the pressure is 0.5MPa, and the volume space velocity of acetylene is 250h-1Under the condition of (1), after the reaction is carried out for 2000 hours, the acetylene conversion rate is 99.37 percent, and the acetaldehyde selectivity is 98.29 percent.
Example 3
Selecting active carbon fiber as carrier with particle size of 50 mesh and specific surface area of 1600m2The pore volume is 2.5 mL/g. At room temperature, at 30ml/min N2Performing plasma treatment under the atmosphere, performing treatment for 1.5h at a current of 3A and a voltage of 20V, taking out, then soaking the activated carbon fiber in a phosphoric acid solution with the mass fraction of 10% at 30 ℃, taking out after soaking for 5h, and drying for later use.
30.35g of dioctyltin and 2.25g of BiCl3Dissolving in 100mL of deionized water, stirring to mix uniformly, dripping the mixture on 100g of activated carbon fiber carrier treated by plasma at 30 ℃, performing action treatment for 2h under the condition of an electrostatic field with the strength of 30kv/cm, taking out the mixture from the electrostatic field, and drying for 15h at 110 ℃ to obtain the tin-based catalyst, wherein the tin loading capacity is 10 percent, and the BiCl is3The loading was 0.1%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 140 ℃, the pressure is 0.01MPa, and the volume space velocity of acetylene is 5h-1Under the condition of (1), after the reaction is carried out for 2000 hours, the acetylene conversion rate is 98.97 percent, and the acetaldehyde selectivity is 99.01 percent.
Example 4
Selecting carbon nano tube as carrier, its grain size is 80 meshes, specific surface area is 600m2The pore volume is 1.5 mL/g. At room temperature, at 60ml/min N2In the atmosphere, enterAnd carrying out plasma treatment at a current of 4A and a voltage of 25V, and taking out for later use after 2h of treatment.
44g of tributyltin acetate and 3.6g of FeCl3Dissolving in 100mL of carbon tetrachloride, stirring to mix uniformly, dripping the mixture on 100g of carbon nano tube treated by plasma at 22 ℃, performing action treatment for 0.8h under the condition of an electrostatic field with the strength of 40kv/cm, taking out from the electrostatic field, and drying for 20h at 80 ℃ to obtain the tin-based catalyst, wherein the tin loading is 15%, and FeCl is3The loading was 1.2%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 200 ℃, the pressure is 1.5MPa, and the volume space velocity of acetylene is 100h-1After 2000h of reaction, the acetylene conversion was 98.39% and the acetaldehyde selectivity was 99.21%.
Example 5
Selecting graphene as a carrier, wherein the particle size of the graphene is 60 meshes, and the specific surface area of the graphene is 2500m2Pore volume 0.3mL/g at room temperature at 40mL/min N2And performing plasma treatment under the atmosphere, treating for 0.25h at a current of 5A and a voltage of 16V, and taking out for later use. .
42.11g of triphenyltin and 0.28g of CaCl2Dissolving in 100mL of diethyl ether, stirring to mix uniformly, dripping the mixture on 100g of graphene treated by plasma at 24 ℃, performing action treatment for 1h under the condition of an electrostatic field with the strength of 50kv/cm, taking out the graphene from the electrostatic field, and drying for 24h at 40 ℃ to obtain the tin-based catalyst, wherein the tin loading is 13 percent, CaCl is added2The loading was 0.1%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 160 ℃, the pressure is 2MPa, and the volume space velocity of acetylene is 500h-1Under the condition of (1), after the reaction is carried out for 2000 hours, the acetylene conversion rate is 99.01 percent, and the acetaldehyde selectivity is 99.04 percent.
Example 6
ZSM-5 molecular sieve is selected as a carrier, the particle size is 70 meshes, and the specific surface area is 600m2The pore volume is 0.5 mL/g. At room temperature, at 20ml/min N2Under the atmosphere, plasma treatment is carried out, the current is 2.5A, the voltage is 18V,after 1.8h of treatment, the mixture is taken out for standby.
Dissolving 43.78g of stannic chloride and 3.81g of KCl in 100mL of tetrahydrofuran, stirring to mix uniformly, dropwise adding the mixed solution onto 100g of ZSM-5 molecular sieve treated by plasma at 28 ℃, performing action treatment for 1.6h under the condition of an electrostatic field with the strength of 25kv/cm, taking out from the electrostatic field, and drying for 16h at 70 ℃ to obtain the tin-based catalyst, wherein the tin loading is 20% and the KCl loading is 2%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 180 ℃, the pressure is 1MPa, and the volume space velocity of acetylene is 400h-1Under the condition of (1), after the reaction is carried out for 2000 hours, the acetylene conversion rate is 99.11 percent, and the acetaldehyde selectivity is 98.34 percent.
Comparative example 1
Comparative example 1 illustrates the non-substitutability of electrostatic field technology in the catalyst preparation process by comparison with example 1.
Selecting columnar active carbon as carrier, with particle diameter of 20 mesh and specific surface area of 1000m2The pore volume is 1 mL/g. At room temperature, at 5ml/min N2And performing plasma treatment under the atmosphere, wherein the current is 1A, the voltage is 10V, and the plasma is taken out for standby after treatment for 0.5 h.
21.89g of tin tetrachloride and 0.21g of ZnCl2Dissolving in 100mL of methanol, stirring to mix uniformly, dripping the mixture on 100g of activated carbon carrier treated by plasma at 20 ℃, and drying for 8h at 70 ℃ to obtain the tin-based catalyst, wherein the tin loading is 10 percent, and ZnCl is used as the catalyst2The loading was 0.1%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the pressure is 0.1MPa, and the volume space velocity of acetylene is 300h-1After 2000h of reaction, the acetylene conversion was 69.30% and the acetaldehyde selectivity was 78.12%.
Comparative example 2
Comparative example 2 illustrates the non-substitutability of plasma technology in the preparation of a catalyst by comparison with example 1.
Selecting columnar activated carbon as carrier with particle size of 20 mesh,specific surface area 1000m2The pore volume is 1 mL/g. .
21.89g of tin tetrachloride and 0.21g of ZnCl2Dissolving in 100mL of methanol, stirring to mix uniformly, dripping the mixed solution onto 100g of activated carbon carrier at 20 ℃, performing action treatment for 0.5h under the condition of an electrostatic field with the strength of 10kv/cm, taking out the solution from the electrostatic field, and drying for 8h at 70 ℃ to obtain the tin-based catalyst, wherein the tin loading is 10 percent, and ZnCl is2The loading was 0.1%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the pressure is 0.1MPa, and the volume space velocity of acetylene is 300h-1After 2000h of reaction, the acetylene conversion was 76.45% and the acetaldehyde selectivity was 78.12%.
Comparative example 3
Comparative example 2 illustrates the effect of nitrogen doping of activated carbon fibers during catalyst preparation by comparison with example 2.
Active carbon fiber is selected as a carrier, the particle size of the carrier is 100 meshes, and the specific surface area is 800m2The pore volume is 0.25 mL/g. At room temperature, at 10ml/min N2In the atmosphere, plasma treatment was carried out at a current of 2A and a voltage of 15V, and the substrate was taken out after 1 hour of treatment.
47.80g of tin dichloride and 2.25g of BiCl3Dissolving in 100mL deionized water, stirring to mix uniformly, dripping the mixture on 100g of activated carbon fiber carrier treated by plasma at 25 ℃, performing action treatment for 1.5h under the condition of an electrostatic field with the strength of 20kv/cm, taking out from the electrostatic field, and drying for 10h at 110 ℃ to obtain the tin-based catalyst, wherein the tin loading capacity is 30 percent, and the BiCl is3The loading was 2%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 110 ℃, the pressure is 0.5MPa, and the volume space velocity of acetylene is 250h-1After 2000h of reaction, the acetylene conversion was 89.51% and the acetaldehyde selectivity was 76.54%.
Comparative example 4
Comparative example 4 illustrates the effect of phosphorus doping of activated carbon fibers in the catalyst preparation process by comparison with example 3.
Selecting active carbon fiber as carrier with particle size of 50 mesh and specific surface area of 1600m2The pore volume is 2.5 mL/g. At room temperature, at 30ml/min N2In the atmosphere, plasma treatment was carried out at a current of 3A and a voltage of 20V for 1.5 hours, and then the substrate was taken out.
30.35g of dioctyltin and 2.25g of BiCl3Dissolving in 100mL of deionized water, stirring to mix uniformly, dripping the mixture on 100g of activated carbon fiber carrier treated by plasma at 30 ℃, performing action treatment for 2h under the condition of an electrostatic field with the strength of 30kv/cm, taking out the mixture from the electrostatic field, and drying for 15h at 110 ℃ to obtain the tin-based catalyst, wherein the tin loading capacity is 10 percent, and the BiCl is3The loading was 0.1%.
The catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 140 ℃, the pressure is 0.01MPa, and the volume space velocity of acetylene is 5h-1After 2000h of reaction, the acetylene conversion was 81.27% and the acetaldehyde selectivity was 69.01%.
Comparative example 5
Comparative example 5 Zn-10Cu/MCM catalyst was prepared according to the document New j. chem.2018,42,6507-6514, and reacted with example 1 under the same reaction conditions, illustrating the superiority of the invention.
The Zn-10Cu/MCM catalyst prepared according to the literature is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the pressure is 0.1MPa, and the volume space velocity of acetylene is 300h-1After 2000 hours of reaction time, the acetylene conversion was 47.21% and the acetaldehyde selectivity was 55.21%.
Comparative example 6
A conventional mercury sulfate-sulfuric acid catalyst was prepared and reacted with example 1 under the same reaction conditions, illustrating the superiority of the invention.
The traditional mercury sulfate-sulfuric acid catalyst is applied to acetylene hydration reaction in a reactor, and the reaction conditions are as follows: the temperature is 150 ℃, the pressure is 0.1MPa, and the volume space velocity of acetylene is 300h-1After 2000h of reaction, the acetylene conversion was 35.56% and the acetaldehyde selectivity was 55.16%.

Claims (6)

1. A preparation method of a tin-based catalyst comprises the following steps:
dissolving a tin-containing precursor and a base metal additive in a solvent, stirring to uniformly mix the precursor and the base metal additive, dripping the mixed solution onto a porous solid carrier at the temperature of 20-30 ℃, carrying out isovolumetric impregnation under the action of an electrostatic field for 0.5-2 hours, and then drying at the temperature of 40-110 ℃ for 8-24 hours to obtain a tin-based catalyst; the base metal auxiliary agent is one or more of Bi, Ba, Fe, Mn, Zn, K, Ca and Ni;
the action conditions of the electrostatic field are as follows: the electric field intensity is 10-50 kv/cm, and the processing time is 0.5-2 h;
the porous solid carrier is selected from one of activated carbon, activated carbon fiber, carbon nano tube, graphene, silicon dioxide, aluminum oxide, titanium dioxide and molecular sieve; wherein the active carbon is columnar carbon or spherical active carbon, the particle size is 20-100 meshes, and the specific surface area is 500-1500 m2The pore volume is 0.25-1.5 mL/g; the activated carbon fiber is processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 500-1600 m2(iv) per gram, the pore volume is 0.25-2.5 mL/g; the carbon nano tube is processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface is 250-1600 m2The pore volume is 0.25-2.5 mL/g; the graphene is processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 500-3000 m2The pore volume is 0.25-2.5 mL/g; the aluminum oxide is gamma-Al2O3And processed into columnar or spherical shape with particle size of 10-100 meshes and specific surface area of 250-800 m2The pore volume is 0.1-1.5 mL/g; the silicon dioxide is processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2The pore volume is 0.1-1.5 mL/g; the titanium dioxide is processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2(iv) per gram, pore volume is 0.1-1.0 mL/g; the molecular sieve is ZSM-5, beta molecular sieve, gamma molecular sieve, 5A molecular sieve, 10X molecular sieve or 13X molecular sieve, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2The pore volume is 0.1-1.8 mL/g;
the porous solid carrierSubjecting the body to plasma treatment under the following conditions: the current is 1-5A, the voltage is 10-25V, and the treatment time is 0.5-2 h; the plasma treatment is carried out at N2Carried out under an atmosphere, N2The flow rate is 5-60 ml/min;
the activated carbon fiber is doped with nitrogen or phosphorus, and the doping process comprises the following steps: preparing a nitrogen-containing or phosphorus-containing precursor into an aqueous solution with the mass fraction of 10-15%, and then soaking the activated carbon fiber in the aqueous solution of the nitrogen-containing or phosphorus-containing precursor for 1-5 hours at the temperature of 30-60 ℃; the nitrogen-containing precursor is ammonium chloride, urea or ethylenediamine, and the phosphorus-containing precursor is phosphoric acid.
2. The method of claim 1, wherein: in the tin-based catalyst, the tin loading amount is 10-30 wt%; the loading capacity of the base metal additive is 0.1-2 wt%.
3. The method of claim 1 or 2, wherein: the tin-containing precursor is one of tin dichloride, dioctyltin, stannic chloride, tributyltin acetate and triphenyltin;
the base metal auxiliary agent is one or a mixture of more of bismuth chloride, barium chloride, ferric chloride, manganese chloride, zinc chloride, potassium chloride, calcium chloride and nickel chloride;
the solvent is one or more of deionized water, absolute ethyl alcohol, tetrahydrofuran, methanol, acetone, diethyl ether, cyclohexane, carbon tetrachloride and benzene.
4. Use of a tin-based catalyst prepared according to the preparation method of claim 1 in the hydration reaction of acetylene to acetaldehyde.
5. The use according to claim 4, characterized in that the use is in particular: the tin-based catalyst is filled in a reactor, and feed gas H is introduced2O and C2H2And reacting under the reaction conditions that the reaction temperature is 100-200 ℃ and the reaction pressure is 0.01-2 MPa to obtain acetaldehyde.
6. The use of claim 5, wherein: the volume airspeed of acetylene is 5-500 h-1。
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