CN108620107B - Catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate and preparation method and application thereof - Google Patents
Catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, and a preparation method and application thereof. The catalyst takes NiM double-element particles as active components and TiO2Is a carrier; the first element of the NiM double-element particles is metal Ni, and the second element M is any one of nonmetal B, P; the support TiO2Has a surface area of 2 to 200m2Per g, pore volume of 2-200cm3Per g, the aperture is 0.05-5 nm; the content of metal Ni in the catalyst is 5 wt% -25 wt%, and the content of element M is 2 wt% -10 wt%; the preparation method of the catalyst comprises the following steps: dissolving a precursor of Ni and a precursor of M in water, uniformly mixing, adding nitric acid to adjust PH, and preparing into a precursor solution; adding carrier TiO2Dipping for more than 5 hours, filtering out the solution and drying to obtain a catalyst precursor; and roasting, reducing and cooling the dried catalyst precursor to obtain the catalyst. The catalyst material of the invention is cheap, the preparation process is simple, and the catalyst is suitable for industrialized synthesis of methyl glycolate.
Description
Technical Field
The invention relates to the field of catalyst chemistry, in particular to a catalyst for synthesizing methyl glycolate through dimethyl oxalate hydrogenation, and a preparation method and application thereof.
Background
Methyl glycolate is a very important intermediate for drug synthesis and organic synthesis, is an excellent solvent for resin, fiber, rubber and the like, is an additive for synthesizing certain lubricating oil to improve pressure resistance and wear resistance, and is also an intermediate for some anticancer drugs. Methyl glycolate as chemical intermediate may be hydrogenated to prepare glycol, hydrolyzed to prepare glycolic acid, carbonylated to prepare malonic diester, ethyl acetoacetate, etc. Methyl glycolate has wide application in chemical industry.
There are many synthetic process routes for preparing and producing methyl glycolate, the Dupont company in the early 60 th century adopts hydration carbonylation and esterification method, the German Hearst company in the 70 th century adopts methyl formate and formaldehyde coupling method, and the early method routes are gradually eliminated due to the aspects of economic benefit, environmental pollution and the like; in 1996, a one-step synthesis method of ethanol and methanol was developed by Mitsui chemical company of Japan, which has mild reaction conditions and high yield, but has expensive raw materials, causes pollution to the atmosphere, and is not suitable for large-scale industrial production. In the 80 th century of 20 th, Mitsubishi, Japan, developed a formaldehyde carbonylation method and an oxalate hydrogenation method, the reaction conditions of the formaldehyde carbonylation method were very strict, the reaction pressure required reached 50MPa, and the corrosion to equipment was severe. The oxalate hydrogenation method has mild reaction conditions, no pollution to the environment, suitability for industrial production, good application prospect, and only immature process and industrial application technology, particularly catalyst application technology of the reaction, need to be further developed. Therefore, there are few companies producing methyl glycolate on an ultra-large scale internationally, and there are no companies producing methyl glycolate on a large scale domestically.
Patent CN200910184925.5 discloses a catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate and a preparation method thereof, wherein the catalyst takes metallic copper as a main active component, silver and manganese as auxiliary active components, and Al2O3 as a carrier; the catalyst has high reaction activity in the reaction of synthesizing methyl glycolate by hydrogenating dimethyl oxalate, high selectivity of methyl glycolate, stable reaction performance, easy control, simple preparation method, easily obtained raw material source, low price, low cost and long service life. However, the content of the noble metal silver adopted by the catalyst reaches 5 wt% -15 wt%, and the price is expensive. In addition, the patent CN201010148290.6 and the patent CN201110190871.0 both improve the preparation scheme of the catalyst, and prepare the Ag/SiO2 catalyst with high activity, so that the yield of methyl glycolate is greatly improved. However, the noble metal Ag is used as a part of the catalyst, so that the catalyst is expensive.
Patent CN201410589395.3 discloses a catalyst with Cu or Cu oxide as active component and composite oxide SiO2 as carrier site, which optimizes the content, structure and type of active component, auxiliary agent and carrier to obtain a catalyst for synthesizing methyl glycolate with high conversion rate and selectivity. However, the preparation method of the catalyst has more steps, more complex process and certain difficulty in industrialization, and the application of the catalyst is restricted.
Disclosure of Invention
The invention relates to a catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate and a preparation method and application thereof, and solves the technical problems that the existing catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate adopts noble metal as an active ingredient and is expensive; the second technical problem to be solved is to provide a preparation method of the catalyst which is effective in solving the first technical problem and simple in preparation process; the third technical problem to be solved is to provide a method for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, which corresponds to one of the technical problems to be solved.
In order to solve the technical problems, the invention adopts the following scheme:
a catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate is characterized in that: the catalyst takes NiM double-element particles as active components and TiO2Is a carrier; the first element of the NiM double-element particles is metal Ni, and the second element M is any one of nonmetal B, P; the support TiO2Has a surface area of 2 to 200m2Per g, pore volume of 2-200cm3Per g, the aperture is 0.05-5 nm; the content of metal Ni in the catalyst is 5 wt% -25 wt%, and the content of element M is 2 wt% -10 wt%.
A preparation method of a catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate comprises the following steps:
step 1, dissolving a precursor of Ni and a precursor of M in water, uniformly mixing, adding nitric acid to adjust pH, and preparing into a precursor solution;
step 2, adding carrier TiO2Dipping for more than 5 hours, filtering out the solution and drying to obtain a catalyst precursor;
and 3, roasting, reducing and cooling the dried catalyst precursor to obtain the catalyst.
Further, in the step 1, the precursor of Ni is a nitrate or acetylacetone complex of Ni, and the precursor of M is one of boric acid, phosphoric acid, and metaphosphoric acid.
Further, in the precursor solution, the precursor concentration of Ni and the precursor concentration of M in step 1 are both 0.5M or more.
Further, the pH of the precursor solution in step 1 is 1 or less.
Further, the carrier TiO in the step 22Completely immersed in the precursor solution.
Further, the carrier TiO2The temperature of dipping in the precursor solution is 25-80 ℃.
Further, the drying temperature in the step 3 is 105-120 ℃; the drying time is 2-5 hours.
Further, the temperature of roasting and reduction in the step 3 is 450-650 ℃, the roasting and reduction time is 2-10 hours respectively, the roasting is carried out in the air, and the reducing agent is hydrogen.
The application of the catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate is characterized in that: reacting methanol solution dissolved with 10-50 wt% of dimethyl oxalate and hydrogen as raw materials with the catalyst in the claim 1, wherein the molar ratio of the hydrogen to the dimethyl oxalate in the reaction is 50-500, the reaction temperature is 200-230 ℃, the reaction pressure is 2-5MPa, and the reaction space velocity is 0.1-0.5h-1。
The catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, the preparation method and the application thereof have the following beneficial effects:
the active component of the catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate uses non-noble metal Ni and non-metal M to interact, and uses an active carrier TiO2The performance of the active component is improved, so that the catalyst still maintains higher activity and higher selectivity, and the catalyst material is cheap, has simple preparation process and is very suitable for industrialized synthesis of methyl glycolate.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to these examples.
Example 1: example 1:
dissolving a certain amount of nickel nitrate and phosphoric acid in water, uniformly mixing, adding a proper amount of nitric acid to adjust the pH to 1, and preparing a precursor solution, wherein the concentration of Ni in the precursor solution is 8M, and the concentration of P in the precursor solution is 4M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at room temperature for 24 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 2 hours, cooled naturally, reduced at 600 ℃ for 5 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 1. In sample 1, the Ni content was 10 wt% and the P content was 4 wt%.
Example 2:
dissolving a certain amount of nickel nitrate and phosphoric acid in water, uniformly mixing, adding a proper amount of nitric acid to adjust the pH to 1, and preparing a precursor solution, wherein the concentration of Ni in the precursor solution is 2M, and the concentration of P in the precursor solution is 1M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at room temperature for 24 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 2 hours, cooled naturally, reduced at 600 ℃ for 5 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 2. Sample 2 had a Ni content of 5 wt% and a P content of 2 wt%.
Example 3:
dissolving a certain amount of nickel nitrate and phosphoric acid inAfter being uniformly mixed in water, an appropriate amount of nitric acid was added to adjust the PH so that the PH became 0.5, thereby preparing a precursor solution containing Ni at a concentration of 14M and P at a concentration of 7M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at normal temperature for 36 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 3 hours, cooled naturally, reduced at 600 ℃ for 6 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 3. Sample 3 had a Ni content of 25 wt% and a P content of 10 wt%.
Example 4:
dissolving a certain amount of nickel nitrate and phosphoric acid in water, uniformly mixing, adding a proper amount of nitric acid to adjust the pH to 1, and preparing a precursor solution, wherein the concentration of Ni contained in the precursor solution is 8M, and the concentration of P contained in the precursor solution is 8M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at normal temperature for 36 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 2 hours, cooled naturally, reduced at 600 ℃ for 5 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 4. Sample 4 had a Ni content of 10 wt% and a P content of 8 wt%.
Example 5:
dissolving a certain amount of nickel nitrate and boric acid in water, uniformly mixing, adding a proper amount of nitric acid to adjust the pH to 1, and preparing a precursor solution, wherein the concentration of Ni contained in the precursor solution is 10M, and the concentration of B contained in the precursor solution is 10M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at room temperature for 24 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 2 hours, cooled naturally, reduced at 600 ℃ for 5 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 5. In sample 5, the Ni content was 10 wt% and the B content was 4 wt%.
Example 6:
dissolving a certain amount of nickel nitrate and boric acid in water, uniformly mixing, adding a proper amount of nitric acid to adjust the pH,the precursor solution was prepared so that PH was 1, and the concentration of Ni contained in the precursor solution was 2M and the concentration of B contained in the precursor solution was 2M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at room temperature for 24 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 2 hours, cooled naturally, reduced at 600 ℃ for 5 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 6, sample 6 having a Ni content of 5 wt% and a B content of 2 wt%.
Example 7:
dissolving a certain amount of nickel nitrate and boric acid in water, uniformly mixing, adding a proper amount of nitric acid to adjust the pH to 0.5, and preparing a precursor solution, wherein the concentration of Ni in the precursor solution is 14M, and the concentration of B in the precursor solution is 7M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at room temperature for 24 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 3 hours, cooled naturally, reduced at 600 ℃ for 6 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 7. Sample 7 had a Ni content of 25 wt% and a B content of 10 wt%.
Example 8:
dissolving a certain amount of nickel nitrate and boric acid in water, uniformly mixing, adding a proper amount of nitric acid to adjust the pH to 1, and preparing a precursor solution, wherein the concentration of Ni contained in the precursor solution is 10M, and the concentration of B contained in the precursor solution is 5M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at room temperature for 24 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 2 hours, cooled naturally, reduced at 600 ℃ for 5 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 8. Sample 8 had a Ni content of 10 wt% and a B content of 2 wt%.
Example 9:
dissolving a certain amount of nickel nitrate in water, uniformly mixing, adding a proper amount of nitric acid to adjust the pH to 1, preparing a precursor solution, and preparing the precursor solution into a concentrated Ni-containing solutionThe degree was 10M. 100ml of the precursor solution are taken and 60ml of TiO are added2The carrier particles were immersed at room temperature for 24 hours, and the solution was filtered off and dried at 115 ℃ for 2 hours to obtain a catalyst precursor. The catalyst precursor was then calcined in air at 600 ℃ for 2 hours, cooled naturally, reduced at 600 ℃ for 5 hours under H2 atmosphere, and cooled naturally to room temperature to give the desired catalyst sample 9. The Ni content in sample 9 was 10 wt%.
The prepared catalyst is used for evaluating the catalytic performance of synthesizing methyl glycolate by dimethyl oxalate hydrogenation in a fixed bed reactor, the inner diameter of the reactor is 25.4mm, the loading amount of the catalyst is 50ml, 50ml of inert ceramic beads are respectively loaded on the upper part and the lower part of a catalyst bed layer, and the temperature of the reactor is controlled in three sections. Hydrogen is used as raw material gas, methanol solution dissolved with 20 percent of dimethyl oxalate by mass fraction is used as raw material liquid, the molar ratio of the hydrogen to the dimethyl oxalate in the reaction is 250, the reaction temperature is 220 ℃, the reaction pressure is 3MPa, and the reaction airspeed is 0.1-0.5h-1。
When the reaction activity of the catalyst was measured, after the synthesis reaction of methyl glycolate continued for 5 hours and stabilized, the product was poured off, the volume of the raw material liquid was measured as the volume of the raw material liquid before the reaction, the reaction was continued for 12 hours while counting the time, and the analysis product was examined by weighing the raw material, the mass and the volume of the product, gas chromatography analysis or the like, to calculate the conversion of dimethyl oxalate and the selectivity of methyl glycolate. The method is an activity test of the catalyst.
Wherein, the conversion rate calculation formula of the dimethyl oxalate is as follows:
method for calculating methyl glycolate selectivity: the methyl glycolate content in the product was directly analyzed by gas chromatography.
The results are shown in table one.
Table one: evaluation results of catalyst Properties
Claims (7)
1. The catalyst for synthesizing methyl glycolate through hydrogenation of dimethyl oxalate is characterized in that the catalyst takes NiM double-element particles as active components and TiO2Is a carrier; the first element of the NiM double-element particles is metal Ni, and the second element M is nonmetal B; the support TiO2Has a surface area of 2 to 200m2Per g, pore volume of 2-200cm3Per g, the aperture is 0.05-5 nm; the content of metal Ni in the catalyst is 5 wt% -25 wt%, and the content of element B is 2 wt% -10 wt%; the preparation method of the catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate comprises the following steps of:
step 1, dissolving a precursor of Ni and a precursor of M in water, uniformly mixing, adding nitric acid to adjust pH, and preparing into a precursor solution;
step 2, adding carrier TiO2Dipping for more than 5 hours, filtering out the solution and drying to obtain a catalyst precursor;
step 3, roasting, reducing and cooling the dried catalyst precursor to obtain the catalyst;
in the step 1, the precursor of Ni is a nitrate or acetylacetone complex of Ni, and the precursor of M is boric acid; the pH value of the precursor solution in the step 1 is 1 or less.
2. The catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate according to claim 1, wherein in the precursor solution, the precursor concentration of Ni and the precursor concentration of M in step 1 are both 0.5M or more.
3. The catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate according to claim 1, wherein: the carrier TiO in the step 22Is completely impregnated inThe precursor solution.
4. The catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate according to claim 1, wherein: the support TiO2The temperature of dipping in the precursor solution is 25-80 ℃.
5. The catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate according to claim 1, wherein: the drying temperature in the step 3 is 105-120 ℃; the drying time is 2-5 hours.
6. The catalyst for the synthesis of methyl glycolate by the hydrogenation of dimethyl oxalate according to any of claims 1 to 5, wherein: the temperature of roasting and reduction in the step 3 is 450-650 ℃, the roasting and reduction time is 2-10 hours respectively, the roasting is carried out in the air, and the reducing agent is hydrogen.
7. The application of catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate is characterized in that methanol solution dissolved with 10-50 wt% of dimethyl oxalate and hydrogen are used as raw materials to react with the catalyst in the claim 1, the molar ratio of the hydrogen to the dimethyl oxalate in the reaction is 50-500, the reaction temperature is 200-230 ℃, the reaction pressure is 2-5MPa, and the reaction space velocity is 0.1-0.5h-1。
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| CN112316983B (en) * | 2020-10-27 | 2023-05-23 | 宁波中科远东催化工程技术有限公司 | Complex iron desulfurization catalyst and preparation method thereof |
| CN114849705A (en) * | 2022-04-28 | 2022-08-05 | 沈阳化工大学 | Preparation method of catalyst for preparing methyl glycolate through selective hydrogenation of dimethyl oxalate |
| CN114797918B (en) * | 2022-05-30 | 2024-02-27 | 安徽工业大学 | Titanium dioxide-based hydrogenation catalyst material, and preparation method and application thereof |
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