A catalyst for catalytically preparing 1,2-propanediol compounds and a preparation method and application thereof

Abstract

The application provides a catalyst for preparing 1,2-propanediol compounds by dehydrating glycerol compounds, and a preparation method and application thereof, and belongs to the field of catalysts. The catalyst has high catalytic activity, good stability and high strength, and has excellent technical effects.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalysts, in particular to a catalyst for catalytically preparing 1,2-propanediol compounds and a preparation method and application thereof. BACKGROUND

[0002] 1,2-propanediol is an important chemical raw material widely used in food, medicine and chemical industry. In recent years, the investment in biodiesel has been on the rise in China, and glycerol, as a major byproduct of biodiesel production, has begun to be overproduced. How to effectively utilize the large amount of glycerol produced in the production of biodiesel has become a hot research topic. Among the many research topics, it is obviously an economic and environmentally friendly method to use catalysts to efficiently convert glycerol into 1,2-propanediol.

[0003] The catalyst plays a crucial role in the process of preparing 1,2-propanediol from glycerol dehydration. As a solid catalyst, it must face the technical problem of shaping on the road to industrialization. Because no matter how the solid catalyst is prepared, it must finally be made into a suitable shape and size to be used in the industrial reactor. The shaping process of the solid catalyst will certainly affect the mechanical strength, reaction performance, mass and heat transfer capacity of the catalyst, and the bed pressure drop when loaded into the reactor. Specific surface area is one of the most important characteristic parameters of solid catalysts. Generally speaking, the larger the specific surface area of the solid catalyst, the larger the area used for catalytic reaction, the stronger the activity, and the higher the production capacity. Therefore, in the shaping process of the catalyst, the focus is on the effective specific surface area of the catalyst, while ensuring that the catalyst has the highest mechanical strength and the pressure drop meets the relevant requirements when loaded into the reactor.

[0004] Different catalyst shaping methods (preparation methods) produce catalysts with different reaction capacities, mechanical strengths, and conversion rates and selectivities of target products. Based on the current research on catalyst use and catalyst shaping, it is urgent to develop a shaping method that enables the catalyst to have high mechanical strength and high catalytic activity. The catalyst prepared by the catalyst shaping method must meet the requirements and standards of industrial catalysts for preparing 1,2-propanediol from glycerol, i.e. in the process of preparing 1,2-propanediol from glycerol, it not only has a high conversion rate of glycerol, but also has a high reaction selectivity of 1,2-propanediol, and can be operated for a long time while maintaining activity. SUMMARY

[0005] To solve the above technical problems, the present application provides the following technical solutions.

[0006] In a first aspect, the present application provides a preparation method of a catalyst for preparing 1,2-propanediol compounds by dehydration of glycerol compounds.

[0007] A method for preparing a catalyst for dehydrating glycerol compounds to produce 1,2-propanediol compounds, characterized in that the method for preparing the catalyst comprises the steps of:

[0008] (1) mixing a catalyst powder with an organic binder, an inorganic binder, and a pore-forming agent, kneading with an aqueous acid solution, drying, crushing, to obtain a crushed mixture;

[0009] (2) mixing the crushed mixture obtained in step (1) with a solid lubricant to obtain a mixture 1, grinding to obtain a mixture 2;

[0010] (3) tabletting and granulating the mixture 2 obtained in step (2), calcining, to obtain the catalyst for dehydrating glycerol compounds to produce 1,2-propanediol compounds.

[0011] In some embodiments, the inorganic binder is selected from at least one of pseudoboehmite, silica sol, bentonite. In some embodiments, the inorganic binder is pseudoboehmite or silica sol.

[0012] In some embodiments, the organic binder is selected from at least one of starch, gum arabic, methyl cellulose, polyvinylpyrrolidone, paraffin wax. In some embodiments, the organic binder is methyl cellulose or polyvinylpyrrolidone.

[0013] In some embodiments, the pore-forming agent is selected from at least one of polyethylene glycol, polyethylene oxide, cetyltrimethylammonium, fatty acid, glyceride. In some embodiments, the pore-forming agent is at least one of polyethylene glycol, polyethylene oxide, cetyltrimethylammonium. In some embodiments, the pore-forming agent is at least one of polyethylene glycol, polyethylene oxide.

[0014] In some embodiments, the molecular weight of the polyethylene glycol is 200-20000. In some embodiments, the molecular weight of the polyethylene glycol is 2000-10000. In some embodiments, the molecular weight of the polyethylene glycol is 6000.

[0015] In some embodiments, the solid lubricant is selected from at least one of talc powder, graphite powder, stearic acid, dry starch, sesbania powder.

[0016] In some embodiments, the aqueous acid solution is at least one of an aqueous nitric acid solution, an aqueous hydrochloric acid solution, and an aqueous citric acid solution. In some embodiments, the aqueous acid solution is an aqueous nitric acid solution.

[0017] In some embodiments, the acid in the aqueous acid solution is present in an amount of 0.1 wt% to 5.0 wt%. In some embodiments, the acid in the aqueous acid solution is present in an amount of 0.1 wt%, 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 4.0 wt%, or 5.0 wt%. In some embodiments, the acid in the aqueous acid solution is present in an amount of 2.0 wt%.

[0018] In some embodiments, the catalyst powder is at least one selected from the group consisting of an aluminum-based catalyst powder, a chromium-based catalyst powder, a barium-based catalyst powder, a zirconium-based catalyst powder, and a yttrium-based catalyst powder.

[0019] In some embodiments, the method for preparing the catalyst powder comprises:

[0020] 1) mixing an active metal precursor copper nitrate, a carrier precursor salt, and water to obtain a mixed solution 1; the active metal precursor copper nitrate is at least one selected from the group consisting of aluminum nitrate, barium nitrate, chromium nitrate, zirconium nitrate, and yttrium nitrate;

[0021] 2) mixing potassium carbonate and water to obtain a solution 2;

[0022] 3) mixing the mixed solution 1 and the solution 2 and stirring to obtain a mixed solution 3;

[0023] 4) after the completion of step 3), increasing the temperature of the mixed solution 3 to 70°C to 80°C and maintaining for 18h to 24h or 20h;

[0024] 5) filtering the mixed solution 3 after the completion of the maintaining in step 4), washing with water to obtain a washed filter cake;

[0025] 6) drying the washed filter cake obtained in step 5) to obtain a dried filter cake;

[0026] 7) calcining the dried filter cake obtained in step 6), then crushing and grinding to obtain the catalyst powder.

[0027] In some embodiments, the active metal precursor copper nitrate, the support precursor salt has a feed mass ratio of (15-25):(20-500). In some embodiments, the active metal precursor copper nitrate, the support precursor salt has a feed mass ratio of (15-25):(50-400). In some embodiments, the active metal precursor copper nitrate, the support precursor salt has a feed mass ratio of (15-25):(60-300). In some embodiments, the active metal precursor copper nitrate, the support precursor salt has a feed mass ratio of 20:50, 20:60, 20:70, 20:80, 20:90, 20:100, 20:150, 20:200, 20:250, 20:300, 20:350, 20:400, 20:450, or 20:500. In some embodiments, the active metal precursor copper nitrate, the support precursor salt has a feed mass ratio of 20:80.

[0028] In some embodiments, the support precursor salt is zirconium nitrate and / or yttrium nitrate, and the active metal precursor copper nitrate, zirconium nitrate, yttrium nitrate has a feed mass ratio of (15-25):(15-500):(0-20). In some embodiments, the support precursor salt is zirconium nitrate and / or yttrium nitrate, and the active metal precursor copper nitrate, zirconium nitrate, yttrium nitrate has a feed mass ratio of (15-25):(30-500):(0-15). In some embodiments, the support precursor salt is zirconium nitrate and / or yttrium nitrate, and the active metal precursor copper nitrate, zirconium nitrate, yttrium nitrate has a feed mass ratio of (15-25):(40-500):(0-15). In some embodiments, the support precursor salt is zirconium nitrate and / or yttrium nitrate, and the active metal precursor copper nitrate, zirconium nitrate, yttrium nitrate has a feed mass ratio of (15-25):(50-500):(0-15). In some embodiments, the support precursor salt is zirconium nitrate and / or yttrium nitrate, and the active metal precursor copper nitrate, zirconium nitrate, yttrium nitrate has a feed mass ratio of (15-25):(60-500):(0-15). In some embodiments, the support precursor salt is zirconium nitrate and / or yttrium nitrate, and the active metal precursor copper nitrate, zirconium nitrate, yttrium nitrate has a feed mass ratio of (15-25):(70-500):(0-15). In some embodiments, the support precursor salt is zirconium nitrate and / or yttrium nitrate, and the active metal precursor copper nitrate, zirconium nitrate, yttrium nitrate has a feed mass ratio of (15-25):(80-500):(0-15). In some embodiments, the support precursor salt is zirconium nitrate and / or yttrium nitrate, and the active metal precursor copper nitrate, zirconium nitrate, yttrium nitrate has a feed mass ratio of 20:70:10.

[0029] In some embodiments, the total content of the carrier precursor salt in the mixed solution 1 is 10wt%-50wt%, calculated based on the total mass of the mixed solution 1. In some embodiments, the total content of the active metal precursor copper nitrate, the carrier precursor salt in the mixed solution 1 is 10wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 45wt% or 50wt%, calculated based on the total mass of the mixed solution 1.

[0030] In some embodiments, the carrier precursor salt is zirconium nitrate and / or yttrium nitrate, and the total content of the zirconium nitrate, the yttrium nitrate in the mixed solution 1 is 10wt%-50wt%, calculated based on the total mass of the mixed solution 1. In some embodiments, the carrier precursor salt is zirconium nitrate and / or yttrium nitrate, and the total content of the zirconium nitrate, the yttrium nitrate in the mixed solution 1 is 10wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 45wt% or 50wt%, calculated based on the total mass of the mixed solution 1.

[0031] In some embodiments, the content of potassium carbonate in the solution 2 is 30wt%-50wt%, calculated based on the total mass of the solution 2. In some embodiments, the content of potassium carbonate in the solution 2 is 30wt%, 35wt%, 40wt%, 45wt% or 50wt%, calculated based on the total mass of the solution 2. In some embodiments, the content of potassium carbonate in the solution 2 is 50wt%, calculated based on the total mass of the solution 2.

[0032] In some embodiments, the mixed solution 1 and the solution 2 in step 3) are mixed at a mass ratio of 1:1-1:1.3.

[0033] In some embodiments, the temperature of the mixed solution 3 is controlled to be 40°C-50°C, and the pH of the mixed solution 3 is controlled to be 8.0-9.0 during the mixing of the mixed solution 1 and the solution 2 in step 3).

[0034] In some embodiments, the calcination temperature of the calcination is 300°C-450°C. In some embodiments, the calcination temperature of the calcination is 300°C, 350°C, 400°C, 420°C, 430°C, 440°C, or 450°C.

[0035] In some embodiments, the calcination time of the calcination is 4h-6h. In some embodiments, the calcination time of the calcination is 4h, 4.5h, 5h, 5.5h, or 6h.

[0036] In some embodiments, the grinding in step 7) is grinding to a particle size of 0.18mm-0.25mm.

[0037] In some embodiments, the drying temperature of step (1) is 90°C-150°C. In some embodiments, the drying temperature of step (1) is 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or 150°C.

[0038] In some embodiments, the drying time of step (1) is 24h-48h. In some embodiments, the drying time of step (1) is 24h, 25h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 40h, 45h, or 48h.

[0039] In some embodiments, the crushing in step (1) is crushing to a particle size of 0.1mm-1.0mm.

[0040] In some embodiments, the grinding in step (2) is grinding to a particle size of 0.01mm-0.85mm.

[0041] In some embodiments, the grinding in step (2) is grinding to a particle size of 0.10mm-0.25mm, 0.25mm-0.45mm, and 0.45mm-0.65mm, respectively, and mixing.

[0042] In some embodiments, the grinding in step (2) is: taking 15wt%-25wt% of the mixed material 1 and grinding to a particle size of 0.10mm-0.25mm, taking 55wt%-65wt% of the mixed material 1 and grinding to a particle size of 0.25mm-0.45mm, and taking 15wt%-25wt% of the mixed material 1 and grinding to a particle size of 0.45mm-0.65mm, and mixing.

[0043] In some embodiments, the grinding in step (2) is: taking 20 wt% of the mixture 1 and grinding to a particle size of 0.10-0.25 mm, taking 60 wt% of the mixture 1 and grinding to a particle size of 0.25-0.45 mm, and taking 20 wt% of the mixture 1 and grinding to a particle size of 0.45-0.65 mm, and mixing.

[0044] In some embodiments, the pressure of the tableting granulation is 1-20 kN. In some embodiments, the pressure of the tableting granulation is 7 kN.

[0045] In some embodiments, the tableting granulation is compressed into cylindrical particles with a diameter of 1-5 mm and a length of 4-8 mm. In some embodiments, the tableting granulation is compressed into cylindrical particles with a diameter of 3 mm and a length of 6 mm.

[0046] In some embodiments, the temperature of the calcination is 250-550 °C. In some embodiments, the temperature of the calcination is 300-500 °C. In some embodiments, the temperature of the calcination is 400 °C. In some embodiments, the temperature of the calcination is 250 °C, 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, or 550 °C.

[0047] In some embodiments, the time of the calcination is 1-20 hours. In some embodiments, the time of the calcination is 1, 2, 3, 4, 5, 5.5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 hours. In some embodiments, the time of the calcination is 5.5 hours.

[0048] In some embodiments, the powder with a particle size of 0.01-0.25 mm in the mixture 2 accounts for 10-30 wt% of the total mass of the mixture 2, the powder with a particle size of 0.25-0.45 mm accounts for 40-70 wt% of the total mass of the mixture 2, and the powder with a particle size of 0.45-0.85 mm accounts for 10-30 wt% of the total mass of the mixture 2.

[0049] In some embodiments, the powder with a particle size of 0.01-0.25 mm in the mixture 2 accounts for 20 wt% of the total mass of the mixture 2, the powder with a particle size of 0.25-0.45 mm accounts for 60 wt% of the total mass of the mixture 2, and the powder with a particle size of 0.45-0.85 mm accounts for 20 wt% of the total mass of the mixture 2.

[0050] In some embodiments, the catalyst powder to organic binder feed mass ratio is 500.0:10.0-500.0:40. In some embodiments, the catalyst powder to organic binder feed mass ratio is 500.0:10.0-500.0:15.0. In some embodiments, the catalyst powder to organic binder feed mass ratio is 500.0:12.5.

[0051] In some embodiments, the catalyst powder to inorganic binder feed mass ratio is 500.0:10.0-500.0:40. In some embodiments, the catalyst powder to inorganic binder feed mass ratio is 500.0:10.0-500.0:15.0. In some embodiments, the catalyst powder to inorganic binder feed mass ratio is 500.0:12.5.

[0052] In some embodiments, the catalyst powder to pore former feed mass ratio is 500.0:5.0-500.0:20.0. In some embodiments, the catalyst powder to pore former feed mass ratio is 500.0:5.0-500.0:10.0. In some embodiments, the catalyst powder to pore former feed mass ratio is 500.0:7.5.

[0053] In some embodiments, the catalyst powder to aqueous acid solution feed mass ratio is 500.0:100.0-500.0:400.0. In some embodiments, the catalyst powder to aqueous acid solution feed mass ratio is 500.0:200.0-500.0:300.0. In some embodiments, the catalyst powder to aqueous acid solution feed mass ratio is 500.0:250.0.

[0054] In some embodiments, the catalyst powder to solid lubricant feed mass ratio is 500.0:10.0-500.0:20.0.

[0055] In some embodiments, the catalyst powder, inorganic binder, organic binder, pore former, solid lubricant, and aqueous acid solution feed mass ratio is (400.0-600.0):(12.5-40.0):(12.5-40.0):(7.5-20.0):(10.0-15.0):(200.0-300.0).

[0056] (200.0-300.0).

[0057] In some embodiments, the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500.0:(12.5-40.0):(12.5-40.0):(7.5-20.0):(10.0-15.0):250.0.

[0058] In some embodiments, the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is silica sol, the organic binder is methyl cellulose, the pore-forming agent is polyethylene glycol, the solid lubricant is talcum powder, and the aqueous acid solution is a 2.0 wt% aqueous nitric acid solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:12.5:12.5:7.5:10:250.

[0059] In some embodiments, the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is pseudo-boehmite, the organic binder is polyvinylpyrrolidone, the pore-forming agent is polyethylene oxide, the solid lubricant is graphite powder, and the aqueous acid solution is a 2 wt% aqueous nitric acid solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:20:20:10:10:250.

[0060] In some embodiments, the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is silica sol, the organic binder is starch, the pore-forming agent is cetyltrimethylammonium, the solid lubricant is graphite powder, and the aqueous acid solution is a 2 wt% aqueous nitric acid solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:12.5:12.5:7.5:10:250.

[0061] In some embodiments, the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is pseudo-boehmite, the organic binder is starch, the pore-forming agent is polyethylene oxide, the solid lubricant is graphite powder, and the aqueous acid solution is a 2 wt% aqueous nitric acid solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:12.5:12.5:7.5:10:250.

[0062] In some embodiments, the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is bentonite, the organic binder is methyl cellulose, the pore-forming agent is polyethylene oxide, the solid lubricant is amaranth powder, and the aqueous acid solution is a 2wt% aqueous nitric acid solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:12.5:12.5:7.5:10:250.

[0063] In some embodiments, the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is pseudo-boehmite, the organic binder is methyl cellulose, the pore-forming agent is polyethylene oxide, the solid lubricant is amaranth powder, and the aqueous acid solution is a 2wt% aqueous hydrochloric acid solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:40:40:20:15:250.

[0064] In some embodiments, the method for preparing the catalyst powder comprises a co-precipitation method.

[0065] In some embodiments, the glycerol compound is glycerol; and the 1,2-propanediol compound is 1,2-propanediol.

[0066] In a second aspect, the present application provides a catalyst prepared by the method according to the first aspect.

[0067] A catalyst prepared by the method according to the first aspect.

[0068] In a third aspect, the present application provides an application of the catalyst prepared by the method according to the first aspect or the catalyst according to the second aspect.

[0069] An application of the catalyst prepared by the method according to the first aspect or the catalyst according to the second aspect in the dehydration of a glycerol compound to prepare a 1,2-propanediol compound.

[0070] In some embodiments, the glycerol compound is glycerol.

[0071] In some embodiments, the 1,2-propanediol compound is 1,2-propanediol.

[0072] In a fourth aspect, the present application provides a method for the dehydration of a glycerol compound to prepare a 1,2-propanediol compound.

[0073] A method for preparing a 1,2-propanediol compound by dehydrating a glycerol compound, comprising: mixing the catalyst prepared by the preparation method of the first aspect or the catalyst of the second aspect with the glycerol compound, and reacting under a pure H2 atmosphere to obtain a 1,2-propanediol compound;

[0074] In some embodiments, the reaction temperature of the reaction is 180-300°C. In some embodiments, the reaction temperature of the reaction is 180°C, 200°C, 210°C, 215°C, 220°C, 225°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, or 300°C.

[0075] In some embodiments, the reaction pressure of the reaction is 1-10 MPa. In some embodiments, the reaction pressure of the reaction is 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, or 10 MPa.

[0076] In some embodiments, the reaction space velocity of the reaction is 0.1-10.0 h-1. -1 -10.0 h -1 In some embodiments, the reaction space velocity of the reaction is 0.1-10.0 h-1. -1 , 0.2 h -1 , 0.3 h -1 , 0.4 h -1 , 0.5 h -1 , 1.0 h -1 , 2.0 h -1 , 3.0 h -1 , 4.0 h -1 , 5.0 h -1 , 6.0 h -1 , 7.0 h -1 , 8.0 h -1 , 9.0 h -1 , or 10.0 h -1 .

[0077] In some embodiments, the glycerol compound is glycerol.

[0078] In some embodiments, the 1,2-propanediol compound is 1,2-propanediol.

[0079] Advantages

[0080] Compared with the prior art, at least one of the following advantages is provided in some embodiments of the present application:

[0081] (1) Compared with the catalysts prepared by using other kneading reagents, other acid aqueous solutions, other particle size ranges of the mixed material 2, other tabletting granulation pressures, other inorganic binders, other organic binders, other pore-forming agents, or other formulations, the catalyst prepared by using the formulation and preparation method of the present application can reach reaction stability faster, has higher glycerol conversion rate, 1,2-propanediol selectivity, and longer reaction stability duration, and has unexpected technical effects.

[0082] (2) The 1,2-propanediol catalyst preparation method of the present application can maximize the improvement of the mechanical strength of the 1,2-propanediol catalyst while having excellent catalytic activity and 1,2-propanediol selectivity.

[0083] (3) The molding method used in the present application is beneficial to improving the storage stability of the catalyst.

[0084] Terminology

[0085] The term "room temperature" means ambient temperature, in some embodiments 15-40°C, in some embodiments 20-35°C, and in some embodiments 25-30°C.

[0086] In the foregoing of the present application, all the numbers disclosed herein are approximate. Based on the numbers disclosed, each number can vary by ±10% or by a reasonable amount as recognized by those skilled in the art, such as ±1%, ±2%, ±3%, ±4%, or ±5%.

[0087] The terms "above", "below", "within", and the like are understood to include the number itself, for example, two or more means ≥ two.

[0088] The term "and / or" should be understood to mean either one of the options or a combination of any two or more of the options.

[0089] The term "wt%" means mass percentage.

[0090] The term "vol%" or "%vol" means volume percentage.

[0091] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine the different embodiments or examples described in the specification and the features of the different embodiments or examples without contradiction. DETAILED DESCRIPTION

[0092] In order for those skilled in the art to better understand the technical solutions of the present application, some non-limiting embodiments are further disclosed below to further illustrate the present application.

[0093] The reagents used in the present application can be purchased from the market or can be prepared by the method described in the present application.

[0094] The "catalyst for dehydrating glycerol compounds to prepare 1,2-propanediol compounds" described in the present application is referred to as "1,2-propanediol catalyst" in the present application.

[0095] Unless otherwise specified, the molecular weight of the polyethylene oxide used in the examples or comparative examples of the present application is 10000, the polyethylene glycol used in the examples or comparative examples of the present application is polyethylene glycol 6000, and the type of polyvinylpyrrolidone is K-30.

[0096] The preparation method of the catalyst powder described in the following examples or comparative examples is as follows:

[0097] 1) Mix the active metal precursors copper nitrate, zirconium nitrate and yttrium nitrate with water to obtain a mixed solution 1; the total content of zirconium nitrate and yttrium nitrate in the mixed solution 1 is 24wt% calculated based on the total mass of the mixed solution 1; the mass ratio of the active metal precursors copper nitrate, zirconium nitrate and yttrium nitrate is 20:70:10;

[0098] 2) Mix potassium carbonate with water to obtain solution 2; the content of potassium carbonate in the solution 2 is 50wt% calculated based on the total mass of the solution 2;

[0099] 3) Mix the mixed solution 1 and the solution 2 in a mass ratio of 1:1.3 and stir; obtain a mixed solution 3; control the temperature of the mixed solution 3 to be 40-50℃ during the mixing process of the mixed solution 1 and the solution 2, and control the pH of the mixed solution 3 to be 8.0-9.0;

[0100] 4) After the completion of the mixing of step 3), the temperature of the mixed solution 3 is increased to 70-80°C and maintained for 20h;

[0101] 5) The mixed solution 3 after the completion of the maintaining in step 4) is filtered and washed with water to obtain a washed filter cake;

[0102] 6) The washed filter cake obtained in step 5) is dried to obtain a dried filter cake;

[0103] 7) The dried filter cake obtained in step 6) is calcined at 450°C for 4h, then crushed and ground to a particle size of 0.18-0.25mm to obtain the catalyst powder;

[0104] Example 1: Preparation of the catalyst

[0105] 500.0g of the catalyst powder, 12.5g of methyl cellulose, 12.5g of silica sol and 7.5g of polyethylene glycol are mixed, and 250g of 2.0% by mass nitric acid aqueous solution is added to knead the materials together. After the materials are sufficiently kneaded and uniformly mixed, the materials are placed in an oven at 120°C and dried for 30h. The dried materials are crushed by a crusher to a particle size of 0.1-1.0mm. 10.0g of talc powder is added and mixed to obtain a mixed material 1. 20wt% of the mixed material 1 is ground to a particle size of 0.10-0.25mm, 60wt% of the mixed material 1 is ground to a particle size of 0.25-0.45mm, and 20wt% of the mixed material 1 is ground to a particle size of 0.45-0.65mm. The mixed material 2 is obtained by mixing the materials, wherein the powder having a particle size of 0.10-0.25mm accounts for 20wt% of the total mass of the mixed material 2, the powder having a particle size of 0.25-0.45mm accounts for 60wt% of the total mass of the mixed material 2, and the powder having a particle size of 0.45-0.65mm accounts for 20wt% of the total mass of the mixed material 2. The mixed material 2 is tabletted and granulated under a pressure of 7kN to obtain cylindrical particles having a diameter of 3mm and a length of 6mm. Finally, the cylindrical particles are calcined at 400°C for 5.5h to obtain the 1,2-propanediol catalyst of Example 1.

[0106] Example 2: Preparation of the catalyst

[0107] 500.0 g of the catalyst powder, 20.0 g of polyvinylpyrrolidone, 20.0 g of pseudoboehmite, and 10.0 g of polyethylene oxide were mixed, and 250 g of the mixture was kneaded with 2.0% by mass of an aqueous nitric acid solution. After the mixture was sufficiently kneaded and uniformly mixed, the mixture was dried in an oven at 120°C for 30 h. The dried mixture was pulverized by a pulverizer to have a particle size of 0.1 mm to 1.0 mm. 10.0 g of graphite powder was added to the mixture, and the mixture was mixed to obtain a mixture 1. 20% by mass of the mixture 1 was ground to have a particle size of 0.10 mm to 0.25 mm, 60% by mass of the mixture 1 was ground to have a particle size of 0.25 mm to 0.45 mm, and 20% by mass of the mixture 1 was ground to have a particle size of 0.45 mm to 0.65 mm. The mixture 2 was obtained by mixing the powders. In the mixture 2, the powder having a particle size of 0.10 mm to 0.25 mm accounted for 20% by mass of the total mass of the mixture 2, the powder having a particle size of 0.25 mm to 0.45 mm accounted for 60% by mass of the total mass of the mixture 2, and the powder having a particle size of 0.45 mm to 0.65 mm accounted for 20% by mass of the total mass of the mixture 2. The mixture 2 was tabletted under a pressure of 7 kN to obtain cylindrical pellets each having a diameter of 3 mm and a length of 6 mm. The cylindrical pellets were calcined at 400°C for 5.5 h to obtain the 1,2-propanediol catalyst of Example 2.

[0108] Example 3: Investigation of an aqueous nitric acid solution

[0109] Based on Example 1, 2.0% by mass of the aqueous nitric acid solution was replaced with 1.0% by mass of an aqueous nitric acid solution, and the other operations were the same as those in Example 1 to obtain the 1,2-propanediol catalyst of Example 3.

[0110] Example 4: Investigation of an aqueous nitric acid solution

[0111] Based on Example 1, 2.0% by mass of the aqueous nitric acid solution was replaced with 3.0% by mass of an aqueous nitric acid solution, and the other operations were the same as those in Example 1 to obtain the 1,2-propanediol catalyst of Example 4.

[0112] Comparative Example 1: Investigation of a kneading solvent

[0113] Based on Example 1, the aqueous nitric acid solution was replaced with deionized water, and the other operations were the same as those in Example 1 to obtain the catalyst of Comparative Example 1.

[0114] Comparative Example 2: Investigation of the concentration of an aqueous acid solution

[0115] Based on Example 1, 2.0% by mass of the aqueous nitric acid solution was replaced with 0.1% by mass of an aqueous nitric acid solution, and the other operations were the same as those in Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 2.

[0116] Example 1: Investigation of the concentration of the aqueous acid solution

[0117] Based on Example 1, the aqueous nitric acid solution with a mass fraction of 2.0% was replaced by an aqueous nitric acid solution with a mass fraction of 5.0%, and other operations were the same as those in Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 3.

[0118] Comparative Example 4: 1,2-propanediol catalyst without adding pore-forming agent

[0119] Different from Example 1, no pore-forming agent was added in the 1,2-propanediol catalyst forming method, specifically as follows:

[0120] 500.0 g of catalyst powder, 12.5 g of methyl cellulose and 12.5 g of silica sol were mixed, and 250 g of aqueous nitric acid solution with a mass fraction of 2.0% was added to knead the materials together. After being sufficiently kneaded and uniformly mixed, the materials were placed in an oven at 120°C for drying for 30 h. The dried materials were crushed by a crusher to a particle size of 0.1 mm-1.0 mm. 10.0 g of talc powder was added and mixed to obtain a mixture 1. 20 wt% of the mixture 1 was ground to a particle size of 0.10 mm-0.25 mm, 60 wt% of the mixture 1 was ground to a particle size of 0.25 mm-0.45 mm, and 20 wt% of the mixture 1 was ground to a particle size of 0.45 mm-0.65 mm. After being mixed, a mixture 2 was obtained, in which the powder with a particle size of 0.10 mm-0.25 mm accounted for 20 wt% of the total mass of the mixture 2, the powder with a particle size of 0.25 mm-0.45 mm accounted for 60 wt% of the total mass of the mixture 2, and the powder with a particle size of 0.45 mm-0.65 mm accounted for 20 wt% of the total mass of the mixture 2. The mixture 2 was tabletted and granulated under a pressure of 7 kN to obtain cylindrical particles with a diameter of 3 mm and a length of 6 mm. Finally, the obtained cylindrical particles were calcined at 400°C for 5.5 h to obtain the 1,2-propanediol catalyst of Comparative Example 4.

[0121] Comparative Example 5: 1,2-propanediol catalyst without adding lubricant

[0122] Different from Example 1, no lubricant was added in the 1,2-propanediol catalyst forming method, specifically as follows:

[0123] 500.0 g of catalyst powder, 12.5 g of methyl cellulose, 12.5 g of silica sol, and 7.5 g of polyethylene glycol were mixed, and 250 g of 2.0% by mass nitric acid aqueous solution was added to knead the materials together. After being sufficiently kneaded and mixed, the materials were dried in an oven at 120°C for 30 h. The dried materials were pulverized by a pulverizer to a particle size of 0.1 mm to 1.0 mm to obtain a mixture 1. 20% by weight of the mixture 1 was ground to a particle size of 0.10 mm to 0.25 mm, 60% by weight of the mixture 1 was ground to a particle size of 0.25 mm to 0.45 mm, and 20% by weight of the mixture 1 was ground to a particle size of 0.45 mm to 0.65 mm. The mixture was mixed to obtain a mixture 2. In the mixture 2, the powder having a particle size of 0.10 mm to 0.25 mm accounted for 20% by weight of the total mass of the mixture 2, the powder having a particle size of 0.25 mm to 0.45 mm accounted for 60% by weight of the total mass of the mixture 2, and the powder having a particle size of 0.45 mm to 0.65 mm accounted for 20% by weight of the total mass of the mixture 2. The mixture 2 was tabletted and granulated under a pressure of 7 kN to obtain cylindrical granules having a diameter of 3 mm and a length of 6 mm. The cylindrical granules were finally calcined at 400°C for 5.5 h to obtain the 1,2-propanediol catalyst of Comparative Example 5.

[0124] Comparative Example 6: 1,2-propanediol catalyst without any additive

[0125] Unlike Example 1, the 1,2-propanediol catalyst was not added with any additive, and the catalyst powder was used for the test. Specifically, the 1,2-propanediol catalyst of Comparative Example 6 was prepared as follows.

[0126] The catalyst powder was ground to a particle size of 0.10 mm to 0.25 mm, 0.25 mm to 0.45 mm, and 0.45 mm to 0.65 mm, respectively. 20 parts by weight of the particles having a particle size of 0.10 mm to 0.25 mm, 60 parts by weight of the particles having a particle size of 0.25 mm to 0.45 mm, and 20 parts by weight of the particles having a particle size of 0.45 mm to 0.65 mm were mixed to obtain the 1,2-propanediol catalyst of Comparative Example 6 without any additive.

[0127] Comparative Example 7: 1,2-propanediol catalyst without inorganic binder

[0128] Unlike Example 1, the 1,2-propanediol catalyst was not added with any additive, and the catalyst powder was used for the test. Specifically, the 1,2-propanediol catalyst of Comparative Example 6 was prepared as follows.

[0129] 500.0 g of the catalyst powder, 12.5 g of methyl cellulose, and 7.5 g of polyethylene glycol were mixed, and 250 g of a 2.0% by mass nitric acid aqueous solution was added to knead the materials together. After being sufficiently kneaded and mixed, the materials were dried in an oven at 120°C for 30 h. The dried materials were pulverized by a pulverizer to a particle size of 0.1 mm to 1.0 mm. Then, 10.0 g of talc powder was added and mixed to obtain a mixture 1. 20% by weight of the mixture 1 was ground to a particle size of 0.10 mm to 0.25 mm, 60% by weight of the mixture 1 was ground to a particle size of 0.25 mm to 0.45 mm, and 20% by weight of the mixture 1 was ground to a particle size of 0.45 mm to 0.65 mm. The mixture was mixed to obtain a mixture 2. In the mixture 2, the powder having a particle size of 0.10 mm to 0.25 mm accounted for 20% by weight of the total mass of the mixture 2, the powder having a particle size of 0.25 mm to 0.45 mm accounted for 60% by weight of the total mass of the mixture 2, and the powder having a particle size of 0.45 mm to 0.65 mm accounted for 20% by weight of the total mass of the mixture 2. The mixture 2 was tabletted and granulated under a pressure of 7 kN to obtain cylindrical granules having a diameter of 3 mm and a length of 6 mm. Finally, the obtained cylindrical granules were calcined at 400°C for 5.5 h to obtain a 1,2-propanediol catalyst of Comparative Example 7 to which no inorganic binder was added.

[0130] Comparative Example 8: 1,2-propanediol catalyst to which no organic binder was added

[0131] Unlike Example 1, no organic binder was added in the 1,2-propanediol catalyst molding method, and the method was as follows:

[0132] 500.0 g of catalyst powder, 12.5 g of silica sol, 7.5 g of polyethylene glycol were mixed, and 250 g of 2.0% by mass nitric acid aqueous solution was added to knead the materials together. After being sufficiently kneaded and mixed, the materials were dried in an oven at 120°C for 30 h. The dried materials were crushed by a crusher to a particle size of 0.1 mm to 1.0 mm. 10.0 g of talc powder was added and mixed to obtain a mixture 1. 20 wt% of the mixture 1 was ground to a particle size of 0.10 mm to 0.25 mm, 60 wt% of the mixture 1 was ground to a particle size of 0.25 mm to 0.45 mm, and 20 wt% of the mixture 1 was ground to a particle size of 0.45 mm to 0.65 mm. The mixture 2 was obtained by mixing the powders. In the mixture 2, the powder having a particle size of 0.10 mm to 0.25 mm accounted for 20 wt% of the total mass of the mixture 2, the powder having a particle size of 0.25 mm to 0.45 mm accounted for 60 wt% of the total mass of the mixture 2, and the powder having a particle size of 0.45 mm to 0.65 mm accounted for 20 wt% of the total mass of the mixture 2. The mixture 2 was tabletted and granulated under a pressure of 7 kN to obtain cylindrical granules having a diameter of 3 mm and a length of 6 mm. The cylindrical granules were calcined at 400°C for 5.5 h to obtain a 1,2-propanediol catalyst of Comparative Example 8 without an organic binder.

[0133] Investigation of the particle size of the mixture 2 in Comparative Example 9

[0134] In Comparative Example 9, the particle size of the mixture 2 after grinding was 0.01 mm to 0.1 mm. Specifically, the particle size of the mixture 2 after grinding was as follows.

[0135] 500.0 g of catalyst powder, 12.5 g of methyl cellulose, 12.5 g of silica sol, 7.5 g of polyethylene glycol were mixed, and 250 g of 2.0% by mass nitric acid aqueous solution was added to knead the materials together. After being sufficiently kneaded and mixed, the materials were dried in an oven at 120°C for 30 h. The dried materials were crushed by a crusher to a particle size of 0.1 mm to 1.0 mm. 10.0 g of talc powder was added and ground to a particle size of 0.85 mm to 1.0 mm to obtain a mixture 2. The mixture 2 was tabletted and granulated under a pressure of 7 kN to obtain cylindrical granules having a diameter of 3 mm and a length of 6 mm. The cylindrical granules were calcined at 400°C for 5.5 h to obtain a 1,2-propanediol catalyst of Comparative Example 9.

[0136] Investigation of the particle size of the mixture 2 in Comparative Example 10

[0137] In Comparative Example 10, the particle size of the mixture 2 after grinding was 0.01 mm to 0.1 mm. Specifically, the particle size of the mixture 2 after grinding was as follows.

[0138] 500.0 g of catalyst powder, 12.5 g of methyl cellulose, 12.5 g of silica sol, and 7.5 g of polyethylene glycol were mixed, and 250 g of 2.0% by mass nitric acid aqueous solution was added to knead the materials together. After being sufficiently kneaded and mixed, the materials were dried in an oven at 120°C for 30 h. The dried materials were crushed by a crusher to a particle size of 0.1 mm to 1.0 mm. 10.0 g of talc powder was added to the crushed materials, and the mixture was ground to a particle size of 0.01 mm to 0.1 mm to obtain mixture 2. The mixture 2 was tabletted and granulated at a pressure of 30 kN to produce cylindrical granules having a diameter of 3 mm and a length of 6 mm. The cylindrical granules were finally calcined at 400°C for 5.5 h to obtain the 1,2-propanediol catalyst of Comparative Example 10.

[0139] Comparative Example 11: Investigation of the pressure for tabletted and granulated

[0140] In Comparative Example 11, the pressure for tabletted and granulated was 30 kN, and the procedure was as follows:

[0141] 500.0 g of catalyst powder, 12.5 g of methyl cellulose, 12.5 g of silica sol, and 7.5 g of polyethylene glycol were mixed, and 250 g of 2.0% by mass nitric acid aqueous solution was added to knead the materials together. After being sufficiently kneaded and mixed, the materials were dried in an oven at 120°C for 30 h. The dried materials were crushed by a crusher to a particle size of 0.1 mm to 1.0 mm. 10.0 g of talc powder was added to the crushed materials, and the mixture was ground to a particle size of 0.01 mm to 0.1 mm to obtain mixture 2. The mixture 2 was tabletted and granulated at a pressure of 30 kN to produce cylindrical granules having a diameter of 3 mm and a length of 6 mm. The cylindrical granules were finally calcined at 400°C for 5.5 h to obtain the 1,2-propanediol catalyst of Comparative Example 10.

[0142] Comparative Examples 12 to 16: Investigation of inorganic binders and organic binders

[0143] 1) Investigation of organic binders:

[0144] Comparative Example 12: Based on the preparation method of Example 1, methyl cellulose was replaced by gum arabic, and the rest of the operations were the same as Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 12.

[0145] Comparative Example 13: Based on the preparation method of Example 1, methyl cellulose was replaced by paraffin wax, and the rest of the operations were the same as Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 13.

[0146] Comparative Example 14: Based on the preparation method of Example 1, methyl cellulose was replaced by starch, and the rest of the operations were the same as Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 14.

[0147] 2) Investigation of inorganic binders

[0148] Comparative Example 15: Based on the preparation method of Example 1, silica sol was replaced by aluminum sol, and the rest of the operations were the same as Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 15.

[0149] Comparative Example 16: Based on the preparation method of Example 1, silica sol was replaced by bentonite, and the rest of the operations were the same as Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 16.

[0150] Comparative Examples 17-18: Investigation of porogen

[0151] Comparative Example 17: Based on the preparation method of Example 1, polyethylene glycol was replaced by polyvinyl alcohol, and the rest of the operations were the same as Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 17.

[0152] Comparative Example 18: Based on the preparation method of Example 1, polyethylene glycol was replaced by cetyltrimethylammonium, and the rest of the operations were the same as Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 18.

[0153] Investigation of the effect of the molding method on stability

[0154] Unlike Example 1, the catalyst powder of Comparative Example 19 was first stored in the accelerated condition (40°C, 75% RH) in the dark for 6 months before testing, specifically:

[0155] The catalyst powder was stored in the accelerated condition (40°C, 75% RH) in the dark for 6 months. Then, the catalyst powder stored in the accelerated condition (40°C, 75% RH) in the dark for 6 months was prepared according to the prescription and preparation method of Example 1 to obtain the 1,2-propanediol catalyst of Comparative Example 19.

[0156] Example 5: Investigation of the effect of the molding method on stability

[0157] The preparation method of the 1,2-propanediol catalyst of Example 5 is prepared according to the prescription and preparation method of Example 1, and then stored in the dark for 6 months under accelerated conditions (40°C, 75% RH) to obtain the 1,2-propanediol catalyst of Example 5.

[0158] Test Example 1: Side pressure strength test, catalytic activity and catalytic stability investigation

[0159] 1) Catalytic activity and catalytic sustainability investigation: 250 g of the 1,2-propanediol catalyst obtained in each of the above examples or comparative examples was respectively taken and subjected to continuous reaction with glycerol in a fixed bed reaction device under the conditions of 220°C, 2 MPa and pure H2 atmosphere, and the reaction space velocity of the glycerol was 0.2 h -1 , to obtain a reaction product. The glycerol conversion rate, 1,2-propanediol selectivity and hydroxyacetone selectivity at different time periods were detected (the detection frequency can be: every 2-3 h for detection before reaching reaction stability, every 5-12 h for detection when the reaction reaches stability, and every 4-6 h for detection after the first decrease in stability data), and the glycerol conversion rate, 1,2-propanediol selectivity and hydroxyacetone selectivity after reaction stability, the time required to reach stability and the duration of reaction stability were calculated using the 1,2-propanediol catalyst of each example and each comparative example, respectively. The results are shown in Table 1.

[0160] The reaction stability refers to that during the reaction stability period, the absolute value of the difference between the glycerol conversion rate and the average value of the glycerol conversion rate during the reaction stability period is within 1.0%, the absolute value of the difference between the 1,2-propanediol selectivity and the average value of the 1,2-propanediol selectivity during the reaction stability period is within 2.0%, and the absolute value of the difference between the hydroxyacetone selectivity and the average value of the hydroxyacetone selectivity during the reaction stability period is within 1.0%.

[0161] The results of the glycerol conversion rate, 1,2-propanediol selectivity and hydroxyacetone selectivity after reaction of the 1,2-propanediol catalyst of each example and each comparative example are shown in Table 1.

[0162] Table 1: Investigation results of catalyst activity and catalytic stability

[0163]

[0164]

[0165] Result analysis: from the results of Table 1, compared with other kneading reagents, other acid aqueous solution concentrations, other mixture 2 particle size ranges, other tabletting granulation pressures, other inorganic binders, other organic binders, other pore-forming agents, or other preparations, the catalyst prepared by the preparation method of the application can reach reaction stability faster, has higher glycerol conversion rate, 1,2-propanediol selectivity, and longer reaction stability duration, and has unexpected technical effects.

[0166] 2) Side pressure strength test: five samples of each of the 1,2-propanediol catalyst samples of each of the above examples and comparative examples were tested for side pressure strength using a compression strength tester, and the average value was taken, and the results are shown in Table 2.

[0167] Table 2: Side pressure strength test results

[0168]

[0169]

[0170] Result analysis:

[0171] From Table 1 and Table 2, it can be seen that the 1,2-propanediol catalyst preparation method of the application can maximize the improvement of the mechanical strength of the 1,2-propanediol catalyst while having excellent catalytic activity and 1,2-propanediol selectivity.

[0172] From the results of Example 1, Comparative Example 19, and Example 5, it can be seen that the preparation method of the application is conducive to improving the stability of the obtained catalyst, and the preparation method of the application has unexpected technical effects.

[0173] Comparative Examples 7-8 do not add inorganic binders and organic binders, respectively. In these two comparative examples, the compression strength and catalytic activity of the 1,2-propanediol catalysts are decreased, which shows that a single binder is difficult to maintain the performance of the catalyst powder after forming, and the lack of either binder will adversely affect the 1,2-propanediol catalyst after forming. At the same time, the use of organic binders and inorganic binders is one of the innovations of the application.

[0174] In Comparative Examples 9-10, relatively finer and relatively coarser catalyst mixture powder particles without particle size gradient ratio were used before tabletting, which caused the compression strength and 1,2-propanediol catalytic performance of the 1,2-propanediol catalyst after forming to decrease. However, the particle size range of the mixture 2 of the application is more conducive to improving the compression strength and catalytic performance of the obtained catalyst.

[0175] Although the pressure of the granulation is greatly increased in Comparative Example 11, the side pressure strength of the 1,2-propanediol catalyst after molding is not greatly increased, and the activity of the 1,2-propanediol catalyst is decreased, thus, compared with the pressure of the tablet granulation, the pressure of the tablet granulation provided by the present application is more beneficial to improve the activity of the obtained 1,2-propanediol catalyst.

[0176] Compared with using other inorganic binders, using the inorganic binder provided by the present application is more beneficial to improve the glycerol conversion rate, 1,2-propanediol selectivity, hydroxyacetone selectivity, and reaction stable duration of the prepared 1,2-propanediol catalyst.

[0177] Compared with using other inorganic binders, using the inorganic binder provided by the present application is more beneficial to improve the glycerol conversion rate, 1,2-propanediol selectivity, hydroxyacetone selectivity, and reaction stable duration of the prepared 1,2-propanediol catalyst.

[0178] Compared with using other inorganic binders, using the inorganic binder provided by the present application is more beneficial to improve the glycerol conversion rate, 1,2-propanediol selectivity, hydroxyacetone selectivity, and reaction stable duration of the prepared 1,2-propanediol catalyst.

[0179] The method of the present application has been described by preferred embodiments, and the related personnel can obviously make changes or appropriate changes and combinations to the method and application described herein within the content, spirit and scope of the present application to realize and apply the present application technology. The skilled in the art can refer to the content herein to realize the process parameters. It is particularly pointed out that all similar replacements and changes are obvious to the skilled in the art, and they are considered to be included in the present application.

Claims

1. A method for the preparation of a catalyst for the dehydration of glycerol to 1,2-propanediol, characterized in that, The preparation method of the catalyst comprises the following steps: (1) mixing the catalyst powder with an organic binder, an inorganic binder, a pore-forming agent, kneading with an acid aqueous solution, drying, crushing to obtain a crushed mixture; the inorganic binder is pseudo-boehmite or silica sol; the organic binder is methyl cellulose or polyvinyl pyrrolidone; the pore-forming agent is at least one of polyethylene glycol and polyethylene oxide; the acid aqueous solution is nitric acid aqueous solution or hydrochloric acid aqueous solution; the content of acid in the acid aqueous solution is 2.0wt%; (2) mixing the crushed mixture obtained in step (1) with a solid lubricant to obtain a mixture 1, and grinding to obtain a mixture 2; the solid lubricant is at least one of talc powder, graphite powder and sesbania powder; the grinding is as follows: taking 15wt%-25wt% of the mixture 1 and grinding to a particle size of 0.10mm-0.25mm, taking 55wt%-65wt% of the mixture 1 and grinding to a particle size of 0.25mm-0.45mm, taking 15wt%-25wt% of the mixture 1 and grinding to a particle size of 0.45mm-0.65mm, and mixing; (3) tabletting and granulating the mixture 2 obtained in step (2), and calcining to obtain the catalyst for preparing 1,2-propanediol by dehydration of glycerol; the tabletting and granulating pressure is 1 kN-20 kN; the tabletting and granulating is to compress into cylindrical particles with a diameter of 1mm-5mm and a length of 4mm-8mm; The mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant and the acid aqueous solution is (400.0-600.0):(12.5-40.0):(12.5-40.0):(7.5-20.0):(10.0-15.0):(200.0-300.0); The preparation method of the catalyst powder comprises: 1) mixing the active metal precursor copper nitrate, the carrier precursor salt and water to obtain a mixed solution 1; the carrier precursor salt is at least one of aluminum nitrate, barium nitrate, chromium nitrate, zirconium nitrate and yttrium nitrate; 2) mixing potassium carbonate with water to obtain a solution 2; 3) mixing and stirring the mixed solution 1 and the solution 2 to obtain a mixed solution 3; 4) after the mixing in step 3) is completed, the temperature of the mixed solution 3 is increased to 70℃-80℃ for 18h-24h; 5) filtering and washing the mixed solution 3 after the heat preservation in step 4) is completed to obtain a washed filter cake; 6) drying the washed filter cake obtained in step 5) to obtain a dried filter cake; 7) calcining the dried filter cake obtained in step 6), then crushing and grinding to obtain the catalyst powder; The catalyst is applied to the preparation of 1,2-propanediol by dehydration of glycerol, which comprises mixing the catalyst for preparing 1,2-propanediol by dehydration of glycerol with glycerol, and reacting under the condition of pure H2 atmosphere to obtain 1,2-propanediol.

2. The preparation method according to claim 1, wherein the heat preservation time of step 4) in the preparation method of the catalyst powder is 20h.

3. The preparation method according to claim 1, wherein the mass ratio of the active metal precursor copper nitrate to the carrier precursor salt is (15-25):(20-500).

4. The preparation method according to claim 1, wherein the mass ratio of the active metal precursor copper nitrate to the carrier precursor salt is 20:

80.

5. The preparation method according to claim 1, wherein the carrier precursor salt is zirconium nitrate and / or yttrium nitrate; and the mass ratio of the active metal precursor copper nitrate, zirconium nitrate and yttrium nitrate is (15-25):(15-500):(0-20).

6. The preparation method according to claim 1, wherein the carrier precursor salt is zirconium nitrate and / or yttrium nitrate; and the mass ratio of the active metal precursor copper nitrate, zirconium nitrate and yttrium nitrate is 20:70:

10.

7. The preparation method according to claim 1, wherein the content of the carrier precursor salt in the mixed solution 1 is 10wt%-50wt% based on the total mass of the mixed solution 1.

8. The preparation method according to claim 1, wherein the content of potassium carbonate in the solution 2 is 30wt%-50wt% based on the total mass of the solution 2.

9. The preparation method according to claim 1, wherein the mixed solution 1 and the solution 2 are mixed in a mass ratio of 1:1-1:1.3 in step 3).

10. The preparation method according to claim 1, wherein the temperature of the mixed solution 3 is controlled to be 40℃-50℃ and the pH of the mixed solution 3 is controlled to be 8.0-9.0 during the mixing of the mixed solution 1 and the solution 2 in step 3).

11. The preparation method according to claim 1, wherein the calcination temperature of the calcination in step 7) is 300℃-450℃.

12. The preparation method according to claim 1, wherein the calcination time of the calcination in step 7) is 4h-6h.

13. The preparation method according to claim 1, wherein the grinding in step 7) is to a particle size of 0.18mm-0.25mm.

14. The preparation method according to any one of claims 1-13, wherein the drying temperature in step (1) is 90℃-150℃.

15. The preparation method according to any one of claims 1-13, wherein the drying time in step (1) is 24h-48h.

16. The preparation method according to any one of claims 1-13, wherein the crushing in step (1) is to a particle size of 0.1mm-1.0mm.

17. The preparation method according to any one of claims 1-13, wherein the grinding in step (2) is: taking 20wt% of the mixed material 1 and grinding to a particle size of 0.10mm-0.25mm, taking 60wt% of the mixed material 1 and grinding to a particle size of 0.25mm-0.45mm, taking 20wt% of the mixed material 1 and grinding to a particle size of 0.45mm-0.65mm, and mixing.

18. The preparation method according to any one of claims 1-13, wherein the pressure of the tabletting and granulating is 7kN.

19. The preparation method according to any one of claims 1-13, wherein the tableting granulation is tableted into cylindrical particles with a diameter of 3 mm and a length of 6 mm.

20. The preparation method according to any one of claims 1-13, wherein the temperature of the calcination in step (2) is 250-550 °C.

21. The preparation method according to any one of claims 1-13, wherein the temperature of the calcination in step (2) is 400 °C.

22. The preparation method according to any one of claims 1-13, wherein the time of the calcination in step (2) is 1-20 hours.

23. The preparation method according to any one of claims 1-13, wherein the time of the calcination in step (2) is 5.5 hours.

24. The preparation method according to any one of claims 1-13, wherein the powder with a particle size of 0.01-0.25 mm in the mixture 2 accounts for 20 wt% of the total mass of the mixture 2, the powder with a particle size of 0.25-0.45 mm accounts for 60 wt% of the total mass of the mixture 2, and the powder with a particle size of 0.45-0.85 mm accounts for 20 wt% of the total mass of the mixture 2.

25. The preparation method according to any one of claims 1-13, wherein the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500.0:(12.5-40.0):(12.5-40.0):(7.5-20.0):(10.0-15.0):250.

0.

26. The preparation method according to any one of claims 1-13, wherein the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is silica sol, the organic binder is methyl cellulose, the pore-forming agent is polyethylene glycol, the solid lubricant is talc powder, and the aqueous acid solution is a 2.0 wt% nitric acid aqueous solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:12.5:12.5:7.5:10:250; or the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is pseudoboehmite, the organic binder is polyvinylpyrrolidone, the pore-forming agent is polyethylene oxide, the solid lubricant is graphite powder, and the aqueous acid solution is a 2 wt% nitric acid aqueous solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:20:20:10:10:250; or the catalyst powder is a 1,2-propanediol catalyst powder, the inorganic binder is pseudoboehmite, the organic binder is methyl cellulose, the pore-forming agent is polyethylene oxide, the solid lubricant is sesbania powder, and the aqueous acid solution is a 2 wt% hydrochloric acid aqueous solution; the mass ratio of the catalyst powder, the inorganic binder, the organic binder, the pore-forming agent, the solid lubricant, and the aqueous acid solution is 500:40:40:20:15:

250. ​ ​ ​ ​ 27. A catalyst prepared by the preparation method of any one of claims 1-26 for use in the dehydration of glycerol to produce 1,2-propanediol.

28. Use of a catalyst prepared by the preparation method of any one of claims 1-26 or the catalyst of claim 27 for use in the dehydration of glycerol to produce 1,2-propanediol in the dehydration of glycerol to produce 1,2-propanediol. The method of preparing 1,2-propanediol from glycerol by dehydration comprises: The catalyst prepared by the preparation method of any one of claims 1-26 or the catalyst of claim 27 is mixed with glycerol and reacted under a pure H2 atmosphere to obtain 1,2-propanediol.

29. The use according to claim 28, wherein the reaction temperature of the reaction is 180-300 °C.

30. The use according to claim 28, wherein the reaction pressure of the reaction is 1-10 MPa.

31. Use according to claim 28, wherein the reaction has a reaction space velocity of 0.1 h -1 -10.0 h -1 .

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