CN109772389B - Molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol by glycerol hydrogenation, and preparation method and application thereof - Google Patents
Molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol by glycerol hydrogenation, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol by glycerol hydrogenation, and a preparation method and application thereof, wherein the molybdenum sulfide-zirconium phosphate catalyst is prepared by mixing zirconium phosphate and molybdenum sulfide by a ball milling method, and the mass ratio of the zirconium phosphate to the molybdenum sulfide is 0.5-2: 1. The molybdenum sulfide-zirconium phosphate catalyst is used in the reaction of preparing the propenol by gas phase hydrogenation of glycerol, the reaction temperature is controlled to be 185-225 ℃, the hydrogen pressure is 1-3 MPa, the conversion rate of the glycerol after the reaction can reach 49.5% -82.8%, the selectivity of the propenol can reach 40.5%, and the highest space-time yield of the propenol can reach 0.25 g-propenol/g-catalyst/hour.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol by glycerol hydrogenation, and a preparation method and application thereof.
Background
At present, the industrial production route of allyl alcohol mainly comprises four methods of chloropropene hydrolysis, propylene oxide isomerization, acrolein reduction and acetic allyl ester hydrolysis. The chloropropene hydrolysis method can generate a large amount of waste residues in the hydrolysis process; although the propylene oxide isomerization method has the characteristics of simple process, high yield, no corrosion to equipment and the like, the yield is low due to the limitation of the source and price of propylene oxide; the acrolein reduction method has the advantages that chlorine is not needed, but the yield is low, and the problems of high toxicity, easy polymerization and the like of the acrolein are difficult to popularize; the hydrolysis method of acetate propylene ester is a process developed in 1985 by Showa Denko K.K., and has the advantages of mild reaction conditions, stable production and high purity of propylene alcohol. However, the raw material of the production route is the petroleum cracking product, namely propylene, and with the increasing shortage of petroleum resources, the price of propylene is gradually increased and the raw material is in short supply. Therefore, the renewable glycerol is used as the raw material, the one-step method for preparing the propenol with high selectivity has important innovative significance, and the process has high technical and economic values.
The existing reaction process for preparing allyl alcohol by glycerol in one step can be divided into homogeneous reaction and gas-solid phase reaction.
The gas-solid reaction mainly comprises a hydrogen transfer method and a hydrogenolysis method. The hydrogen transfer method uses organic alcohol or glycerin as hydrogen source, the catalyst needs to remove part of hydrogen in the hydrogen source firstly, then the hydrogen is transferred to glycerin molecule in situ, and the processes mainly use iron oxide and molybdenum oxide as catalyst. Yong Liu et al report iron oxide catalysts prepared by a metal salt mixed combustion processGlycerol and various fatty alcohols can be catalyzed to generate allyl alcohol through hydrogen transfer reaction, but the selectivity of the allyl alcohol is only 20-23% (chem.Commun.,46(2010), 1238-1240). Other documents report that iron oxide is used as a catalyst, glycerol is used as a raw material and a hydrogen donor, but at 300-340 ℃, the yield of the allyl alcohol in the process is still lower than 30% (appl.Catal.B-environ.,146(2014) 267-273) for preparing K/Al by adopting a coprecipitation method2O3-ZrO2-FeOxCatalyst, appl.Catal.B-environ, 152-153(2014)117-128, preparation of alkali metal modified Fe by Anhydrous impregnation2O3/Al2O3Catalyst, appl.Catal.A-Gen.,509(2016)130-142 Fe by ion exchange2O3ZSM-5 catalyst). Patent specification with publication number CN 104926604A discloses to contain MoO3-TiO2The composite oxide of the catalyst is used as a catalyst, the selectivity of the propenol can reach more than 80% in the process of preparing the propenol by hydrogenating glycerol in a fixed bed under the conditions that the reaction temperature is 160-240 ℃ and the pressure is 0.1-3.0 MPa, but the used raw material is glycerol methanol solution.
Gas-solid phase hydrogenolysis was only reported in 2016, Santos et al reported the direct conversion of glycerol to propenol at 250 ℃ in a hydrogen atmosphere using CuMoAlO as a catalyst, but with product selectivity below 15% (Catal. Sci. & technol.,6(2016) 4986-5002).
Disclosure of Invention
Aiming at the problems that in the process of directly synthesizing the propenol by the glycerol, the cost of formic acid and organic alcohol as hydrogen donors is high, the catalyst is expensive, toxic and easy to activate, the product is complex, the yield of the propenol is low, the separation process is complicated and the like, the invention provides a molybdenum sulfide-zirconium phosphate catalyst for preparing the propenol by the glycerol hydrogenation, and zirconium phosphate and molybdenum sulfide are mixed by adopting a simple ball milling method to prepare the propenol. The molybdenum sulfide-zirconium phosphate catalyst has an acid site and an oxidation-reduction site, so that the molybdenum sulfide-zirconium phosphate catalyst shows good activity in the reaction of preparing the propenol by hydrogenating gas-phase glycerol, and realizes higher selectivity of the propenol.
A molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol through glycerol hydrogenation is prepared by mixing zirconium phosphate and molybdenum sulfide through a ball milling method, wherein the mass ratio of the zirconium phosphate to the molybdenum sulfide is 0.5-2: 1.
The invention also provides a preparation method of the molybdenum sulfide-zirconium phosphate catalyst, which comprises the steps of firstly preparing zirconium phosphate by a hydrothermal method, and then ball-milling the zirconium phosphate and molybdenum sulfide by a simple ball milling method to prepare the molybdenum sulfide-zirconium phosphate catalyst.
A preparation method of the molybdenum sulfide-zirconium phosphate catalyst comprises the following steps: and ball-milling zirconium phosphate and molybdenum sulfide to obtain a molybdenum sulfide-zirconium phosphate catalyst, wherein the mass ratio of the zirconium phosphate to the molybdenum sulfide is 0.5-2: 1. According to the reaction mechanism (dehydration, dehydration and hydrogenation are needed) of preparing the propenol from the glycerol, the reaction activity of the propenol product is extremely high, the propenol product is easy to be further hydrogenated or polymerized, the dehydration activity of the glycerol can be ensured by a proper amount of zirconium phosphate, the hydrogenation or polymerization of the propenol can be reduced by molybdenum sulfide with weak hydrogenation performance, and the two have obvious synergistic effect.
The ball milling method comprises the following specific steps: and grinding and uniformly mixing zirconium phosphate and molybdenum sulfide, and then carrying out ball milling for 1-3 h at the speed of 250-350 rpm, wherein the mass of agate balls used in the ball milling process is 40-60 times of the sum of the mass of the zirconium phosphate and the mass of the molybdenum sulfide, so as to obtain the molybdenum sulfide-zirconium phosphate catalyst. Because zirconium phosphate and molybdenum sulfide are layered materials, the zirconium phosphate and the molybdenum sulfide can be fully compounded by grinding to form an alternate zirconium phosphate-molybdenum sulfide-zirconium phosphate-molybdenum sulfide composite layered material, so that the synergistic effect of the dehydration-hydrogenation-dehydration functions of the zirconium phosphate-molybdenum sulfide-zirconium sulfide composite layered material can be realized, and the smooth proceeding of the reaction is further ensured.
The molybdenum sulfide-zirconium phosphate catalyst is black powder.
Preferably, the preparation method of zirconium phosphate comprises the following steps:
(1) dropwise adding a phosphoric acid solution into an aqueous solution of zirconium oxychloride octahydrate, and stirring for 0.5-2 hours to obtain a gelatinous precipitate, wherein the molar ratio of P in the phosphoric acid solution to Zr in the aqueous solution of zirconium oxychloride octahydrate is 2-4: 1;
(2) transferring the gelatinous precipitate obtained in the step (1) to a reaction kettle, and carrying out hydrothermal crystallization at 160-200 ℃ for 36-60 h;
(3) centrifuging and washing a product obtained after the hydrothermal crystallization in the step (2) to be neutral, and drying and grinding the product to obtain white powder;
(4) and (4) roasting the white powder obtained in the step (3) for 1-3 hours at 400-500 ℃ in an air atmosphere to obtain zirconium phosphate.
The steps (1) and (2) mainly have the effects of increasing the crystallinity of zirconium phosphate and preventing amorphous materials from being generated.
In the step (4), the roasting mainly has the function of fully removing crystal water in the zirconium phosphate and simultaneously keeping the laminated plate structure unchanged.
Preferably, the heating rate of the roasting is 1-3 ℃/min, so that the laminated plate is prevented from cracking due to too fast heating.
The invention also provides an application of the molybdenum sulfide-zirconium phosphate catalyst in preparation of allyl alcohol by hydrogenation of glycerol.
The molybdenum sulfide-zirconium phosphate catalyst is used for a glycerol gas phase hydrogenation reaction, and the molybdenum sulfide-zirconium phosphate catalyst is activated for 0.5-2 hours at 220-280 ℃ in a hydrogen atmosphere and then subjected to the glycerol gas phase hydrogenation reaction.
The reaction temperature of the glycerol gas-phase hydrogenation reaction is 185-225 ℃, the hydrogen pressure is 1-3 MPa, and the solvent of the glycerol solution is selected from isopropanol, methanol, ethanol or water, wherein the solvent is miscible with glycerol and a product, and the price and safety are considered.
Compared with the prior art, the invention has the main advantages that:
(1) the invention overcomes the problems of high cost of hydrogen donor, expensive catalyst (rhenium, silver and the like), toxicity (chromium and the like), easy inactivation, harsh reaction conditions, low yield of the propenol (gas-solid reaction), complex preparation and separation process, discontinuity (liquid phase reaction) and the like.
(2) The molybdenum sulfide-zirconium phosphate catalyst prepared by the invention is used in the reaction of preparing allyl alcohol by gas phase hydrogenation of glycerol, and the reaction temperature is controlled to be 185-225 ℃, and the hydrogen pressure is controlled to be 1-3 MPa. The conversion rate of the reacted glycerol can reach 49.5-82.8%, the selectivity of the propenol can reach 40.5%, and the space-time yield of the propenol can reach 0.25 g-propenol/g-catalyst/hour at most.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Example 1
Weighing 10.3 g of zirconium oxychloride octahydrate, dissolving the zirconium oxychloride octahydrate in 5 ml of deionized water, stirring for 10 minutes to enable the zirconium oxychloride octahydrate to be uniformly dissolved, slowly and dropwise adding 11.1 g of 85% phosphoric acid solution, wherein the molar ratio of phosphorus to zirconium is 3: 1, mixing and stirring for 1 hour to obtain gelatinous precipitate; transferring the gelatinous precipitate to a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization at 180 ℃ for 48 hours, cooling, washing and centrifuging the obtained product until the pH value is about 7, drying and grinding to obtain white powder; and transferring the white powder into a muffle furnace, calcining the white powder for 2 hours at 450 ℃ in a static air atmosphere, and controlling the heating rate to be 2 ℃/min to obtain a white zirconium phosphate solid. And then 0.4-0.8 g of zirconium phosphate and 0.4-0.8 g of molybdenum sulfide are weighed, namely the mass ratio of the molybdenum sulfide to the zirconium phosphate is controlled to be 1:2, 1:1 and 2:1 during preparation, the mixture is ground in a mortar for 15 minutes and uniformly mixed, then ball milling is carried out at the speed of 300 revolutions per minute for 2 hours, the mass of agate balls in a ball milling tank is 50 times that of a powder sample, and the obtained black powder is a molybdenum sulfide-zirconium phosphate catalyst. Tabletting the catalyst, and screening 40-60 mesh particles.
Weighing 0.2 g of molybdenum sulfide-zirconium phosphate catalyst with 40-60 meshes, filling the catalyst into the middle end of a stainless steel reaction tube with the inner diameter of 6 mm and the length of 540 mm, and sealing the two ends of the stainless steel reaction tube by quartz sand; before the reaction starts, the catalyst is activated for 1 hour under the hydrogen atmosphere at 250 ℃ and the flow rate of 100 ml/min; cooling to the reaction temperature of 205 ℃, adjusting the hydrogen pressure to 3MPa, injecting a glycerol aqueous solution with the mass fraction of 40% into a reaction tube by using a high-pressure pump at the flow rate of 0.01 ml/min, and starting and stabilizing the reaction for 1.5 hours; cooling the reaction product by a cold trap at the temperature of-5 ℃, measuring the obtained liquid product by using capillary gas chromatography, and carrying out quantitative analysis by using an external standard method. The conversion of glycerol and the selectivity to propenol for different molybdenum sulphide to zirconium phosphate mass ratios are shown in table 1.
TABLE 1 conversion of glycerol and selectivity to propenol at different molybdenum sulphide to zirconium phosphate mass ratios
| Mass ratio of molybdenum sulfide to zirconium phosphate | 1:2 | 1:1 | 2:1 |
| Glycerol conversion (%) | 53.6 | 63.7 | 58.3 |
| Propenol selectivity (%) | 8.7 | 9.8 | 8.0 |
Example 2
The same catalyst preparation process as in example 1 was used to prepare a catalyst having a molybdenum sulfide to zirconium phosphate mass ratio of 1:1 and filling and activating the catalyst by the same method, wherein the reaction temperature is 205 ℃, the hydrogen pressure is 3MPa, and glycerol solutions with different solvents and mass fractions of 40% are injected into a reaction tube by a high-pressure pump at the flow rate of 0.01 ml/min, so that the reaction starts and is stable for 1.5 hours; cooling the reaction product by a cold trap at the temperature of-5 ℃, measuring the obtained liquid product by using capillary gas chromatography, and carrying out quantitative analysis by using an external standard method. The conversion of glycerol and selectivity to propenol in the various solvents are shown in table 2.
TABLE 2 conversion of glycerol and selectivity to propenol in different solvents
| Solvent(s) | Isopropanol (I-propanol) | Methanol | Ethanol | Water (W) |
| Glycerol conversion (%) | 64.4 | 57.6 | 81.9 | 63.7 |
| Propenol selectivity (%) | 40.5 | 38.9 | 11.7 | 9.8 |
Example 3
Filling and activating the catalyst by using the same catalyst and the same method in the embodiment 2, wherein the reaction temperature is 185-225 ℃, the hydrogen pressure is 3MPa, injecting the glycerol isopropanol solution with the mass fraction of 40% into a reaction tube by using a high-pressure pump at the flow rate of 0.01 ml/min, and starting and stabilizing the reaction for 1.5 hours; cooling the reaction product by a cold trap at the temperature of-5 ℃, measuring the obtained liquid product by using capillary gas chromatography, and carrying out quantitative analysis by an external standard method. The conversion of glycerol and the selectivity to propenol at different temperatures are shown in table 3.
TABLE 3 conversion of glycerol and selectivity to propenol at different temperatures
| Temperature (. degree.C.) | 185 | 205 | 225 |
| Glycerol conversion (%) | 49.5 | 64.4 | 82.8 |
| Propenol selectivity (%) | 33.4 | 40.5 | 30.5 |
Example 4
Filling and activating the catalyst by using the same catalyst and the same method in the embodiment 2, wherein the reaction temperature is 205 ℃, the hydrogen pressure is 1-3 MPa, injecting the glycerol isopropanol solution with the mass fraction of 40% into a reaction tube by using a high-pressure pump at the flow rate of 0.01 ml/min, and beginning and stabilizing the reaction for 1.5 hours; cooling the reaction product by a cold trap at the temperature of-5 ℃, measuring the obtained liquid product by using capillary gas chromatography, and carrying out quantitative analysis by an external standard method. The conversion of glycerol and selectivity to propenol at different hydrogen pressures are shown in table 4.
TABLE 4 conversion of glycerol and selectivity to propenol at different hydrogen pressures
| Hydrogen pressure (MPa) | 1 | 2 | 3 |
| Glycerol conversion (%) | 36.9 | 44.0 | 64.4 |
| Propenol selectivity (%) | 63.4 | 58.5 | 40.5 |
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (7)
1. The molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol through glycerol hydrogenation is characterized by being prepared by mixing zirconium phosphate and molybdenum sulfide through a ball milling method, wherein the mass ratio of the zirconium phosphate to the molybdenum sulfide is 0.5-2: 1.
2. The molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol by glycerol hydrogenation according to claim 1, wherein the ball milling method comprises the following specific steps: and grinding and uniformly mixing zirconium phosphate and molybdenum sulfide, and then carrying out ball milling for 1-3 h at the speed of 250-350 rpm, wherein the mass of agate balls used in the ball milling process is 40-60 times of the sum of the mass of the zirconium phosphate and the mass of the molybdenum sulfide, so as to obtain the molybdenum sulfide-zirconium phosphate catalyst.
3. The molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol by hydrogenating glycerol according to claim 1 or 2, wherein the preparation method of zirconium phosphate comprises the following steps:
(1) dropwise adding a phosphoric acid solution into an aqueous solution of zirconium oxychloride octahydrate, and stirring for 0.5-2 hours to obtain a gelatinous precipitate, wherein the molar ratio of P in the phosphoric acid solution to Zr in the aqueous solution of zirconium oxychloride octahydrate is 2-4: 1;
(2) transferring the gelatinous precipitate obtained in the step (1) to a reaction kettle, and carrying out hydrothermal crystallization at 160-200 ℃ for 36-60 h;
(3) centrifuging and washing a product obtained after the hydrothermal crystallization in the step (2) to be neutral, and drying and grinding the product to obtain white powder;
(4) and (4) roasting the white powder obtained in the step (3) for 1-3 hours at 400-500 ℃ in an air atmosphere to obtain zirconium phosphate.
4. The molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol through glycerol hydrogenation according to claim 3, wherein in the step (4), the temperature rise rate of roasting is 1-3 ℃/min.
5. The application of the molybdenum sulfide-zirconium phosphate catalyst for preparing the propenol through the hydrogenation of the glycerol according to any one of claims 1 to 4 in the preparation of the propenol through the gas phase hydrogenation of the glycerol is characterized in that the molybdenum sulfide-zirconium phosphate catalyst is activated for 0.5 to 2 hours at 220 to 280 ℃ in a hydrogen atmosphere and then subjected to the gas phase hydrogenation of the glycerol to prepare the propenol.
6. The application of the molybdenum sulfide-zirconium phosphate catalyst for preparing the propenol by hydrogenating the glycerol in the gas phase hydrogenation of the glycerol according to claim 5 is characterized in that the reaction temperature for preparing the propenol by hydrogenating the glycerol in the gas phase is 185-225 ℃, and the hydrogen pressure is 1-3 MPa.
7. The use of the molybdenum sulphide-zirconium phosphate catalyst for the hydrogenation of glycerol to produce propenol according to claim 5 or 6, wherein glycerol solution is used as the raw material, and the solvent of the glycerol solution is selected from isopropanol, methanol, ethanol or water.
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