Supported catalyst as well as preparation method and application thereof

Abstract

The invention discloses a supported catalyst and a preparation method and application thereof.The supported catalyst is prepared from, by mass, 60%-90% of a carrier and a composite oxide of a copper-bismuth metal additive, and in the composite oxide of the copper-bismuth metal additive, the content of copper is 2%-30%, the content of bismuth is 2%-20%, the content of the metal additive is 2%-15%, and the content of the metal additive is 1%-5%. Wherein the metal additive comprises at least one of cerium, manganese, iron, cobalt or zinc. The supported catalyst has high catalytic activity and stability when used for an alkyne-aldehyde reaction, it can be guaranteed that the product propargyl alcohol has high selectivity and yield, the conversion rate of formaldehyde reaches up to 96.77%, and the selectivity and yield of propargyl alcohol can reach up to 63% and 50% with a methanol solution as a reaction solvent. The preparation method of the supported catalyst is simple to operate and easy for industrial production, and has good industrial application value.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and in particular to a supported catalyst and a preparation method and application thereof. Background Art

[0002] Propargyl alcohol is an important chemical raw material. It has a strong coordination carbon-carbon triple bond -C≡C- and a highly polar and hydrophilic terminal hydroxyl group -OH, so it is active and highly reactive. It is widely used in the synthesis of medicines, pesticides, brighteners and rust removers in the electroplating industry and in oil extraction. It can also be used as a solvent, stabilizer for chlorinated hydrocarbons, herbicides and fungicides, etc., and has extremely high added value.

[0003] At present, the main industrial production process of propargyl alcohol is the acetylene aldehyde method, that is, the reaction of formaldehyde solution and acetylene gas under the catalytic action of a copper-based catalyst to generate propargyl alcohol and produce 1,4-butynediol as a by-product. This reaction is a cascade reaction, that is, formaldehyde and acetylene first generate propargyl alcohol, and then propargyl alcohol reacts with formaldehyde to generate 1,4-butynediol. 1,4-Butynediol is also a basic organic chemical raw material, but its economic added value is not as high as that of propargyl alcohol.

[0004] At present, the industrial process of producing propargyl alcohol by the acetylene aldehyde method basically uses water as the reaction solvent, that is, formaldehyde is dissolved in water to prepare a methanol aqueous solution as the reaction raw material for the reaction. Due to the low solubility of acetylene in water, this process has the disadvantages of low propargyl alcohol yield and high yield of by-product 1,4-butynediol. In addition, in the subsequent purification process of propargyl alcohol, propargyl alcohol and water form an azeotrope that is difficult to separate through conventional distillation technology, which increases the process energy consumption.

[0005] Supported copper-bismuth catalyst is currently the most commonly used catalyst for the synthesis of propargyl alcohol by the acetylene aldehyde method in industry. Copper is the active component in the catalyst, while bismuth is the structural and electronic auxiliary. During the reaction, the active component copper (Cu 2+ ) is first reduced by formaldehyde to form Cu + , Cu + It further reacts with acetylene to form an acetylene copper complex catalytic active center. On the one hand, the addition of bismuth can improve the dispersion of copper on the carrier and reduce the particle size of copper. On the other hand, the electronic structure compatibility of copper and bismuth is high and they can form a stable chemical bond. Therefore, the addition of auxiliary bismuth can inhibit the copper + Over-reduction to zero-valent copper during the reaction prevents acetylene from reacting to form polyacetylene, thereby improving the activity and stability of the catalyst.

[0006] However, when the solubility of acetylene in the solution increases, acetylene and formaldehyde will compete for adsorption on the catalyst. A large amount of acetylene adsorbed on the copper acetylene active center may inhibit the adsorption of formaldehyde, thereby affecting the conversion of formaldehyde. In addition, the increase in the amount of acetylene adsorbed on the catalyst surface will lead to an increase in the amount of acetylene polymerized to form polymers. Therefore, the key to achieving efficient preparation of propargyl alcohol by the acetylene-aldehyde method is to rationally design the properties and structure of the catalyst to avoid competitive adsorption of formaldehyde and acetylene when the solubility of acetylene in the solution increases.

[0007] Patent document CN109772352B discloses a catalyst for preparing 1,4-butynediol and co-producing propynyl alcohol, and its preparation method and application. The catalyst has a carrier content of 40-70wt% and a copper-bismuth-magnesium composite oxide content of 30-60wt% based on the weight content of the final catalyst. The copper-bismuth-magnesium composite oxide is loaded on a carrier, and the carrier is at least one of SBA-15 molecular sieve, aluminum oxide, titanium oxide, molecular sieve, zinc oxide, zirconium oxide, and silicon-containing aluminum oxide. However, the invention uses water as the reaction solvent, the solubility of acetylene is low, the selectivity of propynyl alcohol is poor, and the yield is low. Summary of the invention

[0008] The purpose of the present invention is to provide a supported catalyst and a preparation method and application thereof. The supported catalyst of the present invention has high catalytic activity and stability for acetylene-aldehyde reaction, and can ensure that the product propargyl alcohol has high selectivity and yield. The preparation method is simple and suitable for large-scale production.

[0009] The first aspect of the present invention provides a supported catalyst, which comprises 60 to 90% of a carrier and a composite oxide of a copper-bismuth metal additive, based on the mass percentage of the supported catalyst. The composite oxide of the copper-bismuth metal additive has a copper content of 2 to 30%, a bismuth content of 2 to 20%, and a metal additive content of 2 to 15%, wherein the metal additive comprises at least one of cerium, manganese, iron, cobalt or zinc.

[0010] The present invention enhances the adsorption of formaldehyde by adding a metal auxiliary agent other than bismuth, realizes the separation of the adsorption sites of acetylene and formaldehyde, enables acetylene to be adsorbed and activated on the surface of the copper species, and formaldehyde to be adsorbed and activated on the surface of the added metal auxiliary agent, thereby realizing the efficient preparation of propargyl alcohol from acetylene formaldehyde.

[0011] The surfaces of metal oxides such as cerium, manganese, iron, cobalt and zinc have a large number of oxygen vacancies and surface defects, which are conducive to the adsorption of formaldehyde. At the same time, the present invention can change the lattice structure of the metal additives through the strong interaction between the metal additives by adding two or more metal additives, produce lattice distortion, increase the number of oxygen vacancies on the surface of the additives, and form a heterojunction structure between the metal additives, further enhance the adsorption and activation of formaldehyde under the synergistic effect of the metal additives, and thus improve the acetylene-aldehyde reaction performance of the catalyst.

[0012] Preferably, the carrier is an acidic, neutral or alkaline carrier, including at least one of molecular sieves, silica gel, alumina, magnesium oxide or magnesium silicate.

[0013] Preferably, the molecular sieve includes acidic ZSM-5, Y-type, MCM-41 and other silicon-aluminum molecular sieves. The acidic ZSM-5 molecular sieve is obtained by adjusting the acidity and alkalinity of the ZSM-5 molecular sieve to near neutrality by alkali neutralization. The alumina carrier includes basic alumina, neutral alumina and acidic alumina, wherein the acidic alumina is obtained by adjusting its acidity and alkalinity to near neutrality by phosphorus modification.

[0014] The acidity and alkalinity of the carrier surface have a very important influence on the polymerization of acetylene on the catalyst surface. The acid sites on the catalyst surface promote the polymerization of acetylene on the catalyst surface, forming polymers deposited on the catalyst surface, resulting in catalyst deactivation. The present invention can effectively inhibit the polymerization reaction of acetylene and improve the stability of the catalyst by covering the acid sites on the carrier surface to make the carrier close to neutral or using an alkaline carrier.

[0015] Preferably, the supported catalyst comprises, by weight percentage of the supported catalyst, 60-80% of a carrier, 2.5-20% of copper, 2.5-15% of bismuth and 2.5-10% of a metal promoter.

[0016] More preferably, the supported catalyst comprises, by weight percentage of the supported catalyst, 60-70% of a carrier, 3-10% of copper, 3-10% of bismuth and 3-5% of a metal promoter.

[0017] Preferably, the metal promoter is iron, and the content of the carrier in the supported catalyst is 60-85% by mass percentage of the supported catalyst, and the contents of copper, bismuth and iron in the composite oxide of the copper-bismuth metal promoter are 5-15%, 5-10% and 5-10% respectively. The iron promoter has a better effect mainly because the addition of iron has a better dispersion effect on copper on the one hand, and on the other hand, it introduces more holes and defect sites, which is more conducive to the adsorption and activation of formaldehyde.

[0018] Preferably, the metal promoter is iron and manganese, and the carrier content in the supported catalyst is 60-80% by mass percentage of the supported catalyst, and the content of copper, bismuth, iron and manganese in the composite oxide of copper-bismuth metal promoter is 5-15%, 5-10%, 5-10% and 5-10% respectively. The addition of the double promoter will form a heterojunction, further enhance the adsorption and activation of formaldehyde, and thus improve the catalyst's acetylene-aldehyde reaction performance.

[0019] The second aspect of the present invention provides a method for preparing the supported catalyst, comprising the following steps:

[0020] The carrier is impregnated with a solution containing copper, bismuth and a metal promoter precursor, and then dried and calcined to obtain the supported catalyst.

[0021] Preferably, the solution containing copper, bismuth and a metal additive precursor is obtained by dissolving copper, bismuth and a metal additive precursor in a nitric acid solution.

[0022] Preferably, the copper precursor is selected from at least one of copper sulfate, copper nitrate or copper chloride, and the Cu 2+ The molar concentration is 0.33~13.49mol / L.

[0023] Preferably, the bismuth precursor is selected from at least one of bismuth nitrate, bismuth chloride or bismuth acetate, and the solution contains Bi 3+ The molar concentration is controlled at 0.10~2.73mol / L.

[0024] Preferably, the precursor of the metal additive is selected from any one or more of a manganese precursor, an iron precursor, a cobalt precursor, a zinc precursor or a cerium precursor, and the molar concentration of the metal additive in the solution is controlled at 0.15 to 17.63 mol / L.

[0025] Preferably, the manganese precursor is selected from any one of manganese nitrate and manganese chloride, the iron precursor is selected from any one of ferric nitrate and ferric chloride, the cobalt precursor is selected from any one of cobalt nitrate and cobalt chloride, the zinc precursor is selected from any one of zinc nitrate and zinc chloride, and the cerium precursor is selected from cerium nitrate.

[0026] Preferably, the solubility of nitric acid in the solution is 0.34-4.53 mol / L.

[0027] Preferably, the immersion temperature is 20-70° C., the immersion time is 8-16 hours, and after the immersion, the mixture is dried at 90-150° C. for 6-15 hours.

[0028] Preferably, the impregnation may be performed once or multiple times, and the impregnation may be performed by over-volume impregnation, equal-volume impregnation or spraying.

[0029] Preferably, the calcination temperature is 100-800° C., the calcination time is 2-9 hours, and the calcination atmosphere is one or more of air, nitrogen or oxygen.

[0030] Preferably, the calcination is carried out in two stages, the calcination temperature of the first stage is 100-300° C., and the calcination time is 3-5 hours; the calcination temperature of the second stage is 350-600° C., and the calcination time is 2-4 hours.

[0031] The third aspect of the present invention provides the use of the supported catalyst in the preparation of propargyl alcohol by acetylene aldehyde reaction. The catalyst of the present invention can effectively increase the rate of acetylene aldehyde reaction, and the conversion rate of raw materials and the selectivity of propargyl alcohol are both high.

[0032] Preferably, an organic solvent having good solubility for acetylene is used as the reaction solvent for preparing propargyl alcohol from acetylene aldehyde reaction, wherein the organic solvent having good solubility for acetylene includes methanol.

[0033] When the solubility of acetylene in the reaction system is increased, the selectivity of propargyl alcohol will increase. On the contrary, when the solubility of acetylene in the reaction system is reduced, it is conducive to the generation of 1,4-butynediol. The present invention uses methanol, a benign solvent for acetylene, as a reaction solvent for acetylene-aldehyde reaction, which can increase the solubility of acetylene in the reaction system. Formaldehyde in the raw material can react with a large amount of acetylene to generate propargyl alcohol, reduce the residual amount of formaldehyde in the solution, reduce the possibility of the generated propargyl alcohol further reacting with formaldehyde, improve the selectivity of propargyl alcohol, and solve the shortcomings of low yield of propargyl alcohol in the presence of water as the reaction solvent and high energy consumption of subsequent separation and purification process.

[0034] After replacing water with methanol as a solvent, the solubility of acetylene in the solution increases sharply, which can effectively inhibit the formation of butynediol. However, during the reaction, acetylene and formaldehyde will have competitive adsorption on the catalyst surface. The catalyst of the present invention can enhance the adsorption of formaldehyde, realize the separation of acetylene and formaldehyde adsorption sites, and realize the efficient preparation of propynyl alcohol from acetylene formaldehyde.

[0035] Preferably, the method for preparing propargyl alcohol by acetylene aldehyde reaction is to dissolve polyformaldehyde in methanol, a reaction solvent, and depolymerize it at 100-200° C. to obtain a formaldehyde alcohol solution, load the supported catalyst and the formaldehyde alcohol solution into a reactor, and then introduce acetylene gas into the reactor to carry out the reaction.

[0036] Preferably, the reaction temperature is 70-130° C., the reaction pressure is 0.5-2.0 MPa, the initial concentration of the formaldehyde alcohol solution is 5-30 wt %, the mass ratio of the supported catalyst to the formaldehyde alcohol solution is 1:2-10, the stirring rate is 100-800 rpm, and the reaction time is 0.5-7 h.

[0037] Compared with the prior art, the present invention has at least the following beneficial effects:

[0038] (1) The present invention prepares a supported catalyst by adding a metal auxiliary agent (cerium, manganese, iron, cobalt or zinc) other than bismuth, thereby enhancing the adsorption of formaldehyde and achieving the separation of acetylene and formaldehyde adsorption sites, so that acetylene is adsorbed and activated on the surface of the copper species, and formaldehyde is adsorbed and activated on the surface of the added metal auxiliary agent, thereby achieving efficient preparation of propargyl alcohol from acetylene formaldehyde.

[0039] (2) The supported catalyst of the present invention has high catalytic activity and stability for the acetylene aldehyde reaction, and can ensure that the product propargyl alcohol has high selectivity and yield. Compared with the copper bismuth catalyst, the conversion rate of formaldehyde is increased from 28.74% to 96.77%, and the use of methanol solution as the reaction solvent can effectively improve the selectivity of propargyl alcohol, and the selectivity and yield of propargyl alcohol can be as high as 63% and 50%.

[0040] (3) After multiple applications, the supported catalyst of the present invention still maintains a relatively high activity, the formaldehyde conversion rate remains above 93%, and the selectivity and yield of propynyl alcohol both remain above 43%.

[0041] (4) The preparation method of the supported catalyst of the present invention is simple to operate, easy to industrialize and has good industrial application value. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein are used as the usual meanings understood by people with general skills in the field to which the present invention belongs. The words "including" and similar words used in this article mean that the elements or objects appearing before the word include the elements or objects listed after the word and their equivalents, without excluding other elements or objects.

[0043] In view of the problems existing in the prior art, an embodiment of the present invention provides a supported catalyst for producing propargyl alcohol using methanol as a solvent, wherein the supported catalyst comprises a composite oxide of a carrier and a copper-bismuth metal promoter, wherein the metal promoter comprises any one or more of cerium, manganese, iron, cobalt and zinc;

[0044] In terms of the mass percentage of the supported catalyst, the content of the support is 60% to 90%, the content of copper in the composite oxide of copper-bismuth metal additive is 2 to 30%, the content of bismuth is 2 to 20%, and the content of metal additive is 2 to 15% (the content of copper, bismuth, and metal additive is the mass percentage of copper, bismuth, and metal additive in the supported catalyst). In an embodiment of the present invention, a method for preparing a supported catalyst is provided, comprising the following steps:

[0045] S1: impregnating a support with a solution containing copper, bismuth and a metal additive precursor, and controlling the temperature of the solution to be 20 to 70° C.;

[0046] S2: After the loaded carrier is immersed at room temperature for 8 to 16 hours, it is dried at 90 to 150° C. for 6 to 15 hours;

[0047] S3: calcining the dried carrier at 300-800° C. for 2-8 hours to obtain the catalyst, wherein the calcination atmosphere is one or more of air, nitrogen and oxygen.

[0048] In some embodiments of the present invention, the impregnation method does not limit the order in which the copper precursor, the bismuth precursor and the metal additive precursor are loaded onto the carrier, and one, two or three of the copper precursor, the bismuth precursor and the metal additive precursor can be loaded simultaneously.

[0049] In some embodiments of the present invention, the solution containing copper, bismuth and a metal additive precursor is obtained by dissolving copper, bismuth and a metal additive precursor in a nitric acid solution of a certain concentration.

[0050] In some embodiments of the present invention, the copper precursor is selected from any one of copper sulfate, copper nitrate and copper chloride, and the bismuth precursor is selected from any one of bismuth nitrate, bismuth chloride and bismuth acetate.

[0051] In some embodiments of the present invention, the precursor of the metal additive is selected from any one or more of a vanadium precursor, a manganese precursor, an iron precursor, a cobalt precursor, a zinc precursor and a cerium precursor.

[0052] In some embodiments of the present invention, the manganese precursor is selected from any one of manganese nitrate and manganese chloride, the iron precursor is selected from any one of ferric nitrate and ferric chloride, the cobalt precursor is selected from any one of cobalt nitrate and cobalt chloride, the zinc precursor is selected from any one of zinc nitrate and zinc chloride, and the cerium precursor is selected from cerium nitrate.

[0053] In some embodiments of the present invention, in the solution, Cu 2+ The molar concentration of Bi is 0.33~13.49mol / L. 3+The molar concentration of is controlled at 0.10~2.73mol / L, and the molar concentration of metal additive is controlled at 0.15~17.63mol / L.

[0054] In some embodiments of the present invention, the concentration of nitric acid in the solution is controlled at 0.34-4.53 mol / L.

[0055] In some embodiments of the present invention, the impregnation process adopts one or more impregnations, and the impregnation adopts over-volume impregnation, equal-volume impregnation or spraying.

[0056] The embodiment of the present invention provides an application of a supported catalyst, wherein the supported catalyst and a formaldehyde alcohol solution are loaded into an intermittent stirring reactor, acetylene gas is introduced into the reactor to carry out an acetylene-aldehyde reaction to obtain propargyl alcohol, the reaction temperature is 70-130° C., the reaction pressure is 1.0-2.0 MPa, the initial concentration of the formaldehyde alcohol solution is 5wt%-30wt%, the mass ratio of the catalyst dosage to the added formaldehyde alcohol solution is 1:2-1:10, the stirring rate is 100-800rpm, and the reaction time is 0.5-7h.

[0057] In some embodiments of the present invention, the application of the supported catalyst is as follows: the supernatant in the reactor after the previous reaction is transferred out, leaving the supported catalyst after the reaction, adding formaldehyde alcohol solution for stirring, centrifugation, and removing the supernatant for washing three times, and then re-loading the supported catalyst and formaldehyde alcohol solution after the reaction into an intermittent stirring reactor, and introducing acetylene gas to carry out acetylene aldehyde reaction to obtain propargyl alcohol, the reaction temperature is 70-130°C, the reaction pressure is 1.0-2.0MPa, the initial concentration of formaldehyde alcohol solution is 5wt%-30wt%, the mass ratio of the catalyst dosage to the added formaldehyde alcohol solution is 1:2-1:10, the stirring rate is 100-800rpm, and the reaction time is 0.5-7h.

[0058] Example 1

[0059] The preparation method of HZSM-5 carriers with different acidity and alkalinity comprises the following steps:

[0060] Three 20 g HZSM-5 molecular sieve samples were weighed and dispersed in 200 mL of deionized water, and then 80 mL, 100 mL and 120 mL of 0.01 mol / L NaOH solution were added respectively and stirred for 30 min. The mixture was then filtered, washed and dried overnight, and finally calcined at 550 °C for 6 h. The obtained samples were marked as HZSM-5 (80), HZSM-5 (100) and HZSM-5 (120), respectively.

[0061] Example 2

[0062] A method for preparing a HZSM-5 (80) supported copper-bismuth-iron catalyst comprises the following steps:

[0063] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70° C.; 20 g of a dried HZSM-5 (80) carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120° C. oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5° C. / min, and calcined at 120° C. and 400° C. for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0064] Example 3

[0065] A method for preparing a HZSM-5 (100) supported copper-bismuth-iron catalyst comprises the following steps:

[0066] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70° C.; 20 g of dried HZSM-5 (100) carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120° C. oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5° C. / min, and calcined at 120° C. and 400° C. for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0067] Example 4

[0068] A method for preparing a HZSM-5 (120) supported copper-bismuth-iron catalyst comprises the following steps:

[0069] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70° C.; 20 g of dried HZSM-5 (120) carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120° C. oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5° C. / min, and calcined at 120° C. and 400° C. for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0070] Example 5

[0071] The method for regulating the acidic alumina carrier comprises the following steps:

[0072] Three 20 g samples of acidic alumina carrier were weighed and dispersed in aqueous solutions of diammonium phosphate with different concentrations (0.01 g / mL and 0.05 g / mL), respectively. The samples were then stirred at 60°C for 3 hours, filtered and washed until the filtrate was neutral, and then dried at 40°C for 12 hours. Finally, they were calcined at 550°C for 2 hours. The obtained samples were marked as Al2O3(0.01) and Al2O3(0.05), respectively.

[0073] Example 6

[0074] A method for preparing a modified acidic alumina-supported copper-bismuth-iron catalyst comprises the following steps:

[0075] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of dried Al2O3 (0.01) carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0076] Example 7

[0077] A method for preparing a modified acidic alumina-supported copper-bismuth-iron catalyst comprises the following steps:

[0078] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of dried Al2O3 (0.05) carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation for 12 hours at room temperature to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0079] Example 8

[0080] A method for preparing a neutral alumina-supported copper-bismuth-iron catalyst comprises the following steps:

[0081] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry neutral alumina carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0082] Example 9

[0083] A method for preparing a basic alumina-supported copper-bismuth-iron catalyst comprises the following steps:

[0084] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry alkaline alumina carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0085] Example 10

[0086] A method for preparing a macroporous silica gel supported copper-bismuth-cobalt catalyst comprises the following steps:

[0087] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.81 g of cobalt nitrate hexahydrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and cobalt loading of 5%.

[0088] Embodiment 11

[0089] A method for preparing a macroporous silica gel supported copper-bismuth-iron catalyst comprises the following steps:

[0090] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation for 12 hours at room temperature to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0091] Example 12

[0092] A method for preparing a macroporous silica gel supported copper bismuth manganese catalyst comprises the following steps:

[0093] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 7.66 g of manganese nitrate solution (50 wt%) were weighed respectively, and added to 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and manganese loading of 5%.

[0094] Example 13

[0095] A method for preparing a macroporous silica gel-supported copper-bismuth-cerium catalyst comprises the following steps:

[0096] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 6.51 g of cerium nitrate were respectively weighed and added to 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and cerium loading of 5%.

[0097] Embodiment 14

[0098] A method for preparing a macroporous silica gel supported copper bismuth zinc catalyst comprises the following steps:

[0099] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 3.78 g of zinc nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70° C.; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120° C. oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5° C. / min, and calcined at 120° C. and 400° C. for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and zinc loading of 5%.

[0100] Embodiment 15

[0101] A method for preparing a macroporous silica gel supported copper-bismuth-iron catalyst comprises the following steps:

[0102] 37.65 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation for 12 hours at room temperature to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper content of 30% and a bismuth and iron loading of 5%.

[0103] Example 16

[0104] A method for preparing a macroporous silica gel supported copper-bismuth-iron catalyst comprises the following steps:

[0105] 4.47 g of copper nitrate trihydrate, 10.63 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70° C.; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120° C. oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5° C. / min, and calcined at 120° C. and 400° C. for 4 hours and 3 hours, respectively, to obtain a catalyst with a bismuth content of 20% and a copper and iron loading of 5%.

[0106] Embodiment 17

[0107] A method for preparing a macroporous silica gel supported copper-bismuth-iron catalyst comprises the following steps:

[0108] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 16.19 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation for 12 hours at room temperature to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with an iron content of 15% and a copper and bismuth loading of 5%.

[0109] Embodiment 18

[0110] A method for preparing a macroporous silica gel supported copper-bismuth-iron catalyst comprises the following steps:

[0111] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate, 5.10 g of ferric nitrate and 7.66 g of manganese nitrate solution were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70° C.; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120° C. oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5° C. / min, and calcined at 120° C. and 400° C. for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth, iron and manganese loading of 5%.

[0112] Comparative Example 1

[0113] A method for preparing a HZSM-5 supported copper-bismuth-iron catalyst comprises the following steps:

[0114] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70° C.; 20 g of a dried HZSM-5 carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120° C. oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5° C. / min, and calcined at 120° C. and 400° C. for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0115] Comparative Example 2

[0116] A method for preparing an acidic alumina-supported copper-bismuth-iron catalyst comprises the following steps:

[0117] 4.47 g of copper nitrate trihydrate, 2.73 g of bismuth nitrate pentahydrate and 5.10 g of ferric nitrate were weighed respectively, and added into 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry acidic alumina carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was fully aged by impregnation at room temperature for 12 hours to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper, bismuth and iron loading of 5%.

[0118] Comparative Example 3

[0119] A method for preparing a macroporous silica gel-supported copper-bismuth catalyst comprises the following steps:

[0120] 4.22 g of copper nitrate trihydrate and 2.58 g of bismuth nitrate pentahydrate were weighed respectively, and added to 20 mL of 1.2 mol / L nitric acid solution, and an impregnation solution was obtained under stirring at 70°C; 20 g of a dry coarse-porous silica gel carrier was weighed, and the carrier was treated with the prepared impregnation solution by an equal volume impregnation method, and the carrier was immersed for 12 hours at room temperature for sufficient aging to obtain a catalyst wet embryo; the catalyst wet embryo was placed in a 120°C oven and dried for 10 hours to obtain a catalyst dry embryo; the catalyst dry embryo was placed in a muffle furnace and calcined at a heating rate of 5°C / min, and calcined at 120°C and 400°C for 4 hours and 3 hours, respectively, to obtain a catalyst with a copper and bismuth loading of 5%.

[0121] Catalyst performance evaluation

[0122] The catalysts prepared in Examples 2 to 18 and Comparative Examples 1 to 3 were subjected to an acetylene-aldehyde reaction using methanol as a solvent. The steps of the acetylene-aldehyde reaction are as follows:

[0123] 10g of catalyst and 24g of 10% formaldehyde alcohol solution by mass were added to the reactor, and acetylene gas was introduced into the reactor to carry out acetylene-aldehyde reaction to obtain products of propargyl alcohol and 1,4-butynediol. Heating and stirring were turned on at room temperature, and the reaction temperature was raised to 90°C at a rate of 3°C / min. Acetylene gas was introduced to increase the pressure by 1.8MPa and react for 5h. After stopping the reaction, the catalyst and the reaction liquid were separated, and the anhydrous sodium sulfite titration method and formaldehyde content were analyzed, and the propargyl alcohol and 1,4-butynediol content were analyzed by gas chromatography to obtain the formaldehyde conversion rate, propargyl alcohol selectivity and propargyl alcohol yield. The specific results are shown in Table 1. Among them, the formaldehyde alcohol solution was obtained by dissolving polyformaldehyde in the reaction solvent methanol and depolymerizing at 180°C.

[0124] Comparative Example 4

[0125] The acetylene-aldehyde reaction using water as solvent comprises the following steps:

[0126] 10g of the catalyst in Example 11 and 24g of a 10% formaldehyde aqueous solution were added to a reactor, and acetylene gas was introduced into the reactor to perform an acetylene-aldehyde reaction to obtain products of propargyl alcohol and 1,4-butynediol. Heating and stirring were started at room temperature, and the reaction temperature was raised to 90°C at a rate of 3°C / min. Acetylene gas was introduced to increase the pressure by 1.8MPa and react for 5h. After stopping the reaction, the catalyst and the reaction liquid were separated, and the formaldehyde content was analyzed by anhydrous sodium sulfite titration method, and the propargyl alcohol and 1,4-butynediol contents were analyzed by gas chromatography to obtain the formaldehyde conversion rate, propargyl alcohol selectivity and propargyl alcohol yield. The specific results are shown in Table 1.

[0127] Application of catalyst: The catalyst in Example 11 was tested for the number of times it was recycled. The supernatant in the reactor after each reaction was transferred out, leaving the supported catalyst after the reaction. After adding formaldehyde alcohol solution, stirring, centrifuging, and removing the supernatant for washing three times, the supported catalyst and formaldehyde alcohol solution after the reaction were re-loaded into an intermittent stirring reactor, heating and stirring were turned on at room temperature, the reaction temperature was raised to 90°C at a rate of 3°C / min, acetylene gas was introduced to increase the pressure by 1.8MPa, and the reaction was stopped for 5 hours. This was repeated for a total of 5 times of the alkyne-aldehyde reaction. The specific results are shown in Table 2.

[0128] As can be seen from Table 2, after the catalyst in Example 11 has been subjected to five consecutive acetylation reactions using methanol as solvent, the catalyst still maintains a relatively high selectivity and yield of propynyl alcohol, indicating that the supported catalyst of the present invention has good catalytic activity and stability.

[0129] Table 1 Catalyst performance evaluation results

[0130] Formaldehyde conversion rate% Propynol selectivity % Propynol yield% Example 2 62.14 55.32 26.92 Example 3 70.22 59.35 30.06 Example 4 74.92 65.92 34.11 Example 6 65.76 51.05 27.32 Example 7 70.33 47.10 29.75 Example 8 83.97 50.91 38.27 Example 9 85.73 57.83 42.48 Example 10 88.71 57.47 29.73 Embodiment 11 96.77 61.32 49.66 Example 12 91.94 48.90 41.96 Example 13 93.10 44.58 38.51 Embodiment 14 87.17 47.44 37.31 Embodiment 15 93.25 54.78 40.34 Example 16 74.99 56.77 43.18 Embodiment 17 80.25 58.37 41.47 Embodiment 18 94.75 62.94 49.99 Comparative Example 1 42.53 53.15 18.27 Comparative Example 2 39.64 38.91 13.82 Comparative Example 3 28.74 85.42 20.55 Comparative Example 4 97.33 21.82 12.66

[0131] Table 2 Evaluation results of the application performance of the catalyst of Example 11

[0132] Number of applications Formaldehyde conversion rate% Propynol selectivity % Propynol yield% 1st time 96.77 61.32 49.66 2nd 100.00 58.79 47.44 3rd 96.77 50.02 40.55 4th 93.33 51.62 41.32 5th 93.33 43.03 34.92

[0133] Although the implementation methods of the present invention are described in detail above, it is obvious to those skilled in the art that various modifications and variations can be made to these implementation methods. However, it should be understood that such modifications and variations are within the scope and spirit of the present invention described in the claims. Moreover, the present invention described herein may have other implementation methods and may be implemented or realized in a variety of ways.

Claims

1. A supported catalyst, characterized in that The supported catalyst comprises 60-90% of a carrier and a composite oxide of a copper-bismuth metal additive, in which the content of copper, the content of bismuth and the content of the metal additive are 2-30%, 2-20% and 2-15%, respectively, and the metal additive comprises at least one of cerium, manganese, iron, cobalt and zinc.

2. The supported catalyst according to claim 1, characterized in that The carrier is an acidic, neutral or alkaline carrier, including at least one of molecular sieves, silica gel, alumina, magnesium oxide or magnesium silicate.

3. The supported catalyst according to claim 2, characterized in that The molecular sieve includes acidic ZSM-5, Y-type or MCM-41 silicon-aluminum molecular sieve, wherein the acidity and alkalinity of the ZSM-5 molecular sieve are adjusted to near neutrality by alkali neutralization method; And / or, the alumina carrier includes basic alumina, neutral alumina or acidic alumina, wherein the acidic alumina is adjusted to a value close to neutral by phosphorus modification.

4. The supported catalyst according to any one of claims 1 to 3, characterized in that The metal auxiliary agent is iron, the content of the carrier in the supported catalyst is 60-85%, and the contents of copper, bismuth and iron in the composite oxide of the copper-bismuth metal auxiliary agent are 5-15%, 5-10% and 5-10% respectively.

5. The supported catalyst according to any one of claims 1 to 3, characterized in that The metal additives are iron and manganese, the carrier content in the supported catalyst is 60-80%, and the contents of copper, bismuth, iron and manganese in the composite oxide of the copper-bismuth metal additive are 5-15%, 5-10%, 5-10% and 5-10% respectively.

6. The method for preparing a supported catalyst according to any one of claims 1 to 5, comprising the following steps: The carrier is impregnated with a solution containing copper, bismuth and a metal promoter precursor, and then dried and calcined to obtain the supported catalyst.

7. The method for preparing a supported catalyst according to claim 6, characterized in that: The solution containing copper, bismuth and metal additive precursors is obtained by dissolving the copper, bismuth and metal additive precursors in nitric acid solution; Wherein, the copper precursor is selected from at least one of copper sulfate, copper nitrate or copper chloride, and the Cu 2+ The molar concentration is 0.33~13.49mol / L; The bismuth precursor is selected from at least one of bismuth nitrate, bismuth chloride or bismuth acetate, and the solution contains Bi 3+ The molar concentration is 0.10~2.73mol / L; The precursor of the metal auxiliary agent is selected from any one or more of a precursor of manganese, a precursor of iron, a precursor of cobalt, a precursor of zinc or a precursor of cerium, and the molar concentration of the metal auxiliary agent in the solution is 0.15-17.63 mol / L.

8. The method for preparing a supported catalyst according to claim 6 or 7, characterized in that: The impregnation temperature is 20-70°C, the impregnation time is 8-16 hours, and after the impregnation, the mixture is dried at 90-150°C for 6-15 hours; the roasting temperature is 100-800°C, and the roasting time is 2-9 hours.

9. Use of the supported catalyst according to any one of claims 1 to 5 in the preparation of propynyl alcohol by reaction of acetylenic aldehydes.

10. The use according to claim 9, characterized in that: An organic solvent having good solubility for acetylene is used as a reaction solvent for preparing propargyl alcohol by acetylene-aldehyde reaction, wherein the organic solvent having good solubility for acetylene includes methanol.

11. The use according to claim 10, characterized in that: The application method is as follows: dissolving polyformaldehyde in methanol, depolymerizing at 100-200°C to obtain a formaldehyde alcohol solution; loading the supported catalyst and the formaldehyde alcohol solution into a reaction kettle, and then introducing acetylene gas into the reaction kettle to react.

12. The use according to claim 11, characterized in that: The reaction temperature is 70-130° C., the reaction pressure is 0.5-2.0 MPa, the initial concentration of the formaldehyde alcohol solution is 5-30 wt %, the mass ratio of the supported catalyst to the formaldehyde alcohol solution is 1:2-10, and the reaction time is 0.5-7 h.