CN118162134A - Catalyst for preparing methyl glycine and glycine from methyl glycolate, and preparation method and application thereof - Google Patents

Catalyst for preparing methyl glycine and glycine from methyl glycolate, and preparation method and application thereof Download PDF

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CN118162134A
CN118162134A CN202410213429.2A CN202410213429A CN118162134A CN 118162134 A CN118162134 A CN 118162134A CN 202410213429 A CN202410213429 A CN 202410213429A CN 118162134 A CN118162134 A CN 118162134A
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catalyst
glycine
carrier
metal
preparing
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赵建平
王亚红
杨东元
李鸿雄
孙育滨
孙涛
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NORTHWEST UNIVERSITY
Shaanxi Yanchang Xida Advanced Technology Research Institute Co ltd
Shaanxi Yanchang Petroleum Group Co Ltd
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NORTHWEST UNIVERSITY
Shaanxi Yanchang Xida Advanced Technology Research Institute Co ltd
Shaanxi Yanchang Petroleum Group Co Ltd
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Abstract

The invention discloses a catalyst for preparing glycine methyl ester and glycine from methyl glycolate, a preparation method and application thereof, wherein the catalyst is a supported metal catalyst and consists of a catalyst carrier and metal supported on the carrier, the metal is at least one of Co, ir, pd, ni, ru, cu, and the carrier is at least one of SiO 2、Al2O3、CeO2、ZrO2、TiO2; the weight ratio of the metal to the carrier is 0.01-35%. The catalyst has high stability, low preparation cost, no problems of easy decomposition, difficult recycling and the like; meanwhile, the invention provides a novel coal chemical route for preparing glycine methyl ester and glycine, and the intermediate glycolic acid of the coal-to-glycol device is used for replacing the toxic or extremely toxic raw materials used in the traditional glycine synthesis, so that the invention has the advantages of wide raw material sources, low price, safety, no toxicity, environmental protection and the like.

Description

Catalyst for preparing methyl glycine and glycine from methyl glycolate, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of glycine preparation, and particularly relates to a catalyst for preparing glycine methyl ester and glycine from methyl glycolate, and a preparation method and application thereof.
Background
Glycine, also known as glycine, is the simplest amino acid in the institution, and is an important chemical intermediate widely used in the fields of medicine, food, feed and pesticides.
The existing glycine synthesis methods mainly comprise chloroacetic acid ammonolysis, schterkey method, hydantoin method, biological method and the like. The chloroacetic acid ammonolysis method is to take chloroacetic acid and ammonia water as raw materials, and carry out ammonolysis reaction under the action of a catalyst urotropine to generate glycine and ammonium chloride; the process generates a large amount of inorganic salt ammonium chloride, the product is not easy to purify, and simultaneously generates a large amount of wastewater rich in ammonium chloride and formaldehyde, which is not environment-friendly, and the catalyst is easy to decompose and difficult to recycle, so that the production cost is high. The Schtrek method is characterized in that formaldehyde, sodium cyanide and ammonium chloride are used as starting materials, methylene aminoacetonitrile is generated by reaction, aminoacetonitrile sulfate is generated by further decomposition reaction in the presence of sulfuric acid and ethanol, barium hydroxide is used for decomposition to obtain glycine barium salt, and finally sulfuric acid is added to precipitate barium, and glycine crystals are obtained by filtration, concentration and cooling; the method has the advantages of complex synthetic process route, strict operation condition requirement, complex desalting process, high safety risk, and the raw material sodium cyanide is a highly toxic chemical. The hydantoin method takes hydroxy acetonitrile, ammonia and carbon dioxide as raw materials to synthesize and hydrolyze to produce glycine; the process raw material hydroxyacetonitrile has poor thermal stability and is easy to decompose at high temperature and high pressure, so that the glycine yield is reduced and byproducts are increased. The biological method takes glycinonitrile as a raw material, and the glycinonitrile aqueous solution is subjected to hydrolysis reaction under the action of microbial enzyme, so as to be converted into glycine. However, the method has the defects of low enzyme activity, large microbial demand, low glycine yield and the like.
Chinese patent CN 111495373A also discloses a catalyst for preparing methyl glycine and glycine from methyl glycolate, which is prepared by mixing metal with a vitrified silica carrier under nitrogen atmosphere, heating to melt, centrifuging to obtain a bimetal-glass layered eutectic, and drawing wire; however, the preparation method needs high temperature of 1600-1800 ℃ when heating to melt, has high temperature, high cost and difficult industrialization in industry, and the catalyst has poor stability and low repeated use rate.
Therefore, the catalyst with low cost and good stability is provided and has important significance in preparing methyl glycine and glycine from methyl glycolate.
Disclosure of Invention
The invention provides a catalyst for preparing methyl glycine and methyl glycine from dimethyl oxalate semi-hydrogenation product methyl glycolate serving as a glycol intermediate in coal chemical industry, and a preparation method and application thereof, and the catalyst has the advantages of low raw material cost, concise process, environmental protection, high conversion rate and product selectivity, good stability and the like in the process of preparing glycine.
Firstly, the invention provides a catalyst for preparing glycine methyl ester and glycine from methyl glycolate, wherein the catalyst is a supported metal catalyst and consists of a catalyst carrier and metal supported on the carrier, the metal is at least one of Co, ir, pd, ni, ru, cu, and the carrier is at least one of SiO 2、Al2O3、CeO2、ZrO2、TiO2; the weight ratio of the metal to the carrier is 0.01-35%.
Preferably, the carrier is at least one of CeO 2、ZrO2、TiO2.
Preferably, the metal comprises 0.03-30% by weight of the carrier. More preferably, the metal comprises 0.05-20% by weight of the support.
Preferably, the metal is Cu.
Secondly, the invention also provides a preparation method of the catalyst for preparing glycine methyl ester and glycine from methyl glycolate, which comprises the following steps:
(1) Preparing a carrier:
(1.1) mixing a solution of a carrier precursor with an alkaline solution, and stirring to obtain a suspension;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 80-200 ℃ for reaction for 12-30h;
(1.3) cooling to room temperature, centrifuging, washing with water, drying, and roasting to obtain the carrier;
(2) Load metal:
(2.1) adding metal salt corresponding to the metal into a solvent, and stirring at room temperature until the metal salt is dissolved to obtain a metal salt solution;
(2.2) adding a carrier to the metal salt solution, and stirring until the solvent is completely volatilized;
(2.3) roasting to obtain the catalyst.
Preferably, when the support is SiO 2, the corresponding support precursor is a silicate; when the carrier is Al 2O3、CeO2、ZrO2、TiO2, the corresponding carrier precursor is a soluble metal salt corresponding to the metal contained in the carrier.
Preferably, the soluble metal salt corresponding to the metal contained in the carrier is any one of nitrate, acetate, carbonate, phosphate and chloride; the alkaline solution is any one of ammonia water, sodium hydroxide and potassium hydroxide; the molar ratio of the carrier precursor to the alkaline substance in the alkaline solution is (0.01-1): (1-100).
Preferably, in the step (2), the metal salt corresponding to the metal is acetate, chloride or nitrate thereof, and the solvent is acetone or ethanol.
Preferably, the drying conditions are drying at 60-120 ℃ for 5-20 hours; the roasting condition is that roasting is carried out for 1-10h under the air atmosphere and the temperature is raised to 300-600 ℃.
More preferably, the drying conditions are drying at 80-100 ℃ for 10-16 hours; the roasting condition is that roasting is carried out for 3-5 hours under the air atmosphere and the temperature is raised to 450-550 ℃.
Preferably, the temperature is raised to 100-180 ℃ in the step (1.2) for reaction for 20-24 hours.
Preferably, the temperature rising rate of the temperature rising is 1-15 ℃/min. More preferably, the temperature rise rate of the temperature rise according to the present invention is 3 to 5 ℃/min.
Finally, the invention also provides a method for preparing glycine methyl ester and glycine from methyl glycolate, which comprises the following steps: the catalyst provided by the invention is filled into a fixed bed reactor, the catalyst is reduced under the hydrogen atmosphere, and after the catalyst is regulated to the reaction temperature, nitrogen is used for pressurizing to the reaction pressure; methyl glycolate and liquid ammonia are mixed and then enter a preheater, and after preheating, the mixture is introduced into a reactor for reaction; wherein the reaction temperature is 150-320 ℃ and the reaction pressure is 0.1-25.0MPa.
Preferably, the mass airspeed of the methyl glycolate is 0.05-4h -1, and the molar ratio of the liquid ammonia to the methyl glycolate is 20-40:1; the reduction condition is that the reduction is carried out for 3-4 hours under normal pressure and at 200-300 ℃, and the flow rate of hydrogen is 30-100mL/min.
The invention has the advantages that:
(1) The invention provides a novel coal chemical route for preparing glycine methyl ester and glycine, which replaces traditional glycine synthesis with poisonous or highly poisonous chloroacetic acid, potassium cyanide/sodium cyanide, hydrogen cyanide and the like with coal glycol plant intermediate glycolic acid, thus having the advantages of wide raw material sources, low price, safety, no toxicity, environmental protection and the like;
(2) Compared with the traditional glycine synthesis process, the method has the advantages of better atomic economy, shorter process route and lower equipment investment;
(3) Secondly, compared with the chloroacetic acid ammonolysis method commonly used at home, various ammonium salts which are difficult to separate are not generated in the ammonification reaction process of the raw materials, so that the product refining cost is lower and the product quality is higher;
(4) The method is easy for continuous industrial production, and the provided catalyst has high stability, low preparation cost, and no problems of easy decomposition, difficult recycling and the like.
Detailed Description
Example 1
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier CeO 2 and metal Pd supported on the carrier, wherein the metal accounts for 1.3% of the weight of the carrier; the catalyst is expressed as Pd/CeO 2.
2. The catalyst for preparing glycine methyl ester from methyl glycolate is prepared by the following steps:
(1) Preparing a carrier:
(1.1) dissolving 1.96 g Ce (NO 3)3·6H2 O is dissolved in 40 mL deionized water, dropwise adding NaOH solution into the solution, and stirring the solution for 30 minutes to obtain a suspension, wherein the NaOH solution is a solution formed by dissolving 16.88 g NaOH in 30 mL deionized water;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 180 ℃ at 5 ℃/min for reaction for 24 hours;
(1.3) cooling to room temperature, centrifuging, washing with water to ph=7, drying at 80 ℃ for 16 hours, placing in a muffle furnace, heating to 500 ℃ at 5 ℃/min, and air-roasting for 4 hours to obtain the carrier;
(2) Load metal:
(2.1) 10.6 mg Pd (OAc) 2 was added to 5.0. 5.0 mL acetone and stirred at room temperature until dissolved to give a metal salt solution;
(2.2) adding the carrier obtained in the step (1) into the metal salt solution, and stirring until the acetone is completely volatilized;
(2.3) heating to 400 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and air roasting to obtain the catalyst 4h.
Example 2
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier ZrO 2 and metal Cu supported on the carrier, wherein the metal accounts for 15.3% of the weight of the carrier; the catalyst is denoted Cu/ZrO 2.
2. The catalyst for preparing glycine methyl ester from methyl glycolate is prepared by the following steps:
(1) Preparing a carrier:
(1.1) 2.58 g ZrO (NO 3)2·2H2 O is dissolved in 40 mL deionized water, naOH solution is added dropwise into the solution and stirred for 30min to obtain suspension, wherein the NaOH solution is a solution formed by dissolving 16.88 g NaOH in 30 mL deionized water;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 100 ℃ at 5 ℃/min for reaction for 24 hours;
(1.3) cooling to room temperature, centrifuging, washing with water to ph=7, drying at 80 ℃ for 16 hours, placing in a muffle furnace, heating to 500 ℃ at 5 ℃/min, and air-roasting for 4 hours to obtain the carrier;
(2) Load metal:
(2.1) 0.693 g Cu (NO 3)2·3H2 O was added to 5.0. 5.0 mL acetone and stirred at room temperature until dissolved to give a metal salt solution;
(2.2) adding the carrier obtained in the step (1) into the metal salt solution, and stirring until the acetone is completely volatilized;
(2.3) heating to 400 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and air roasting to obtain the catalyst 4h.
Example 3
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier CeO 2 and metal Ni supported on the carrier, wherein the metal accounts for 17.8% of the weight of the carrier; the catalyst is denoted as Ni/CeO 2.
2. The catalyst for preparing glycine methyl ester from methyl glycolate is prepared by the following steps:
(1) Preparing a carrier:
(1.1) dissolving 1.96 g Ce (NO 3)3·6H2 O is dissolved in 40 mL deionized water, dropwise adding NaOH solution into the solution, and stirring the solution for 30 minutes to obtain a suspension, wherein the NaOH solution is a solution formed by 36 g NaOH dissolved in 30 mL deionized water;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 180 ℃ at 5 ℃/min for reaction for 24 hours;
(1.3) cooling to room temperature, centrifuging, washing with water to ph=7, drying at 80 ℃ for 16 hours, placing in a muffle furnace, heating to 500 ℃ at 5 ℃/min, and air-roasting for 4 hours to obtain the carrier;
(2) Load metal:
(2.1) 0.53 g Ni (NO 3)2 was added to 5.0. 5.0 mL acetone and stirred at room temperature until dissolved to give a metal salt solution;
(2.2) adding the carrier obtained in the step (1) into the metal salt solution, and stirring until the acetone is completely volatilized;
(2.3) heating to 400 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and air roasting to obtain the catalyst 4h.
Example 4
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier SiO 2 and metal Ni supported on the carrier, wherein the metal accounts for 13.9% of the weight of the carrier; the catalyst is denoted as Ni/SiO 2.
2. The catalyst for preparing glycine methyl ester from methyl glycolate is prepared by the following steps:
(1) Preparing a carrier:
(1.1) dissolving 3.7 g tetraethyl orthosilicate in 40mL deionized water, dropwise adding NaOH solution into the solution, and stirring the solution for 30min to obtain suspension; wherein the NaOH solution is a solution formed by dissolving 16.88 g NaOH in 30 mL deionized water;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 180 ℃ at 5 ℃/min for reaction for 24 hours;
(1.3) cooling to room temperature, centrifuging, washing with water to ph=7, drying at 80 ℃ for 16 hours, placing in a muffle furnace, heating to 500 ℃ at 5 ℃/min, and air-roasting for 4 hours to obtain the carrier;
(2) Load metal:
(2.1) adding 0.48 gNi (NO 3)2 to 5.0 (mL) acetone, stirring at room temperature until the solution is dissolved to obtain a metal salt solution;
(2.2) adding the carrier obtained in the step (1) into the metal salt solution, and stirring until the acetone is completely volatilized;
(2.3) heating to 400 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and air roasting to obtain the catalyst 4h.
Example 5
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier SiO 2 and metal Cu supported on the carrier, wherein the metal accounts for 25.1% of the weight of the carrier; the catalyst is denoted Cu/SiO 2.
2. In preparing the catalyst, 1.01 gCu (NO 3)2·3H2 O instead of 0.48 gNi (NO 3)2) was used in step (2) in the same manner as in example 4.
Example 6
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier CeO 2 and metal Co supported on the carrier, wherein the metal accounts for 21% of the weight of the carrier; the catalyst is represented by Co/CeO 2.
2. In preparing the catalyst, 1.10 g Co (NO 3)2·6H2 O instead of 10.6 mg Pd (OAc) 2) was used in step (2) with the same preparation as in example 1.
Example 7
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier Al 2O3 and metal Cu supported on the carrier, wherein the metal accounts for 27% of the weight of the carrier; the catalyst is denoted as Cu/Al 2O3.
2. The catalyst for preparing glycine methyl ester from methyl glycolate is prepared by the following steps:
(1) Preparing a carrier:
(1.1) dissolving 3.5 g AlCl 3 in 40 mL deionized water, dropwise adding NaOH solution into the solution, and stirring for 30min to obtain a suspension; wherein the NaOH solution is a solution formed by dissolving 16.88 g NaOH in 30 mL deionized water;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 180 ℃ at 5 ℃/min for reaction for 24 hours;
(1.3) cooling to room temperature, centrifuging, washing with water to ph=7, drying at 80 ℃ for 16 hours, placing in a muffle furnace, heating to 500 ℃ at 5 ℃/min, and air-roasting for 4 hours to obtain the carrier;
(2) Load metal:
(2.1) adding 0.9 g Cu (NO 3)2·3H2 O to 5.0. 5.0 mL acetone, stirring at room temperature until dissolved, to obtain a metal salt solution;
(2.2) adding the carrier obtained in the step (1) into the metal salt solution, and stirring until the acetone is completely volatilized;
(2.3) heating to 450 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and air roasting to obtain the catalyst 4h.
Example 8
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier CeO 2 and metal Ru supported on the carrier, wherein the weight ratio of the metal to the carrier is 1.8%; the catalyst is expressed as Ru/CeO 2.
2. In preparing the catalyst, 8.2 mgRuCl 2 was used in step (2) instead of 10.6 mg Pd (OAc) 2, with the same procedure as in example 1.
Example 9
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier CeO 2 and metal Cu supported on the carrier, wherein the metal accounts for 23% of the weight of the carrier; the catalyst is denoted as Cu/CeO 2.
2. In preparing the catalyst, 0.85 g Cu (NO 3)2·3H2 O instead of 10.6 mg Pd (OAc) 2) was used in step (2) in the same manner as in example 1.
Example 10
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier CeO 2 and metal Ir supported on the carrier, wherein the weight ratio of the metal to the carrier is 1.8%; the catalyst is expressed as Ir/CeO 2.
2. In preparing the catalyst, 22.3 mg H 2IrCl2 was used in step (2) instead of 10.6 mg Pd (OAc) 2, with the same procedure as in example 1.
Example 11
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier TiO 2 and metal Cu supported on the carrier, wherein the metal accounts for 31% of the weight of the carrier; the catalyst is expressed as Cu/TiO 2.
2. The catalyst for preparing glycine methyl ester from methyl glycolate is prepared by the following steps:
(1) Preparing a carrier:
(1.1) dissolving 3.31 g TiCl 4 in 40mL deionized water, dropwise adding NaOH solution into the solution, and stirring for 30min to obtain a suspension; wherein the NaOH solution is a solution formed by dissolving 16.88 g NaOH in 30 mL deionized water;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 180 ℃ at 5 ℃/min for reaction for 24 hours;
(1.3) cooling to room temperature, centrifuging, washing with water to ph=7, drying at 80 ℃ for 16 hours, placing in a muffle furnace, heating to 500 ℃ at 5 ℃/min, and air-roasting for 4 hours to obtain the carrier;
(2) Load metal:
(2.1) 1.1g of Cu (NO 3)2·3H2 O was added to 5.0. 5.0 mL of acetone, and stirred at room temperature until dissolved, to obtain a metal salt solution;
(2.2) adding the carrier obtained in the step (1) into the metal salt solution, and stirring until the acetone is completely volatilized;
(2.3) heating to 400 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and air roasting to obtain the catalyst 4h.
Example 12
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier TiO 2 and metal Ru supported on the carrier, wherein the metal accounts for 2.3% of the weight of the carrier; the catalyst is expressed as Ru/TiO 2.
2. In preparing the catalyst, 40.1 mgRuCl 2 was used instead of 1.1 g Cu (NO 3)2·H2 O) in step (2), otherwise the same preparation as in example 11.
Example 13
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier ZrO 2 and metal Cu supported on the carrier, wherein the weight ratio of the metal to the carrier is 0.01%; the catalyst is denoted Cu/ZrO 2.
2. The catalyst for preparing glycine methyl ester from methyl glycolate is prepared by the following steps:
(1) Preparing a carrier:
(1.1) 2.58 g ZrO (NO 3)2·2H2 O is dissolved in 40 mL deionized water, naOH solution is dropwise added into the solution and stirred for 30min to obtain suspension, wherein the NaOH solution is 38.65g of NaOH solution formed by dissolving 30 mL deionized water;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 80 ℃ at 15 ℃/min for reaction for 30 hours;
(1.3) cooling to room temperature, centrifuging, washing with water to ph=7, drying at 60 ℃ for 20 hours, placing in a muffle furnace, heating to 300 ℃ at 15 ℃/min, and air-roasting for 10 hours to obtain the carrier;
(2) Load metal:
(2.1) adding 0.63 mg Cu (NO 3)2·3H2 O to 5.0. 5.0 mL ethanol, stirring at room temperature until dissolved, to obtain a metal salt solution;
(2.2) adding the carrier obtained in the step (1) into the metal salt solution, and stirring until the acetone is completely volatilized;
(2.3) heating to 300 ℃ in a muffle furnace at a heating rate of 15 ℃/min, and roasting in air for 10 h to obtain the catalyst.
Example 14
1. The catalyst is a supported metal catalyst, and consists of a catalyst carrier ZrO 2 and metal Cu supported on the carrier, wherein the metal accounts for 35% of the weight of the carrier; the catalyst is denoted Cu/ZrO 2.
2. The catalyst for preparing glycine methyl ester from methyl glycolate is prepared by the following steps:
(1) Preparing a carrier:
(1.1) 2.58 g ZrO (NO 3)2·2H2 O is dissolved in 40mL deionized water, naOH solution is added dropwise into the solution and stirred for 30min to obtain suspension, wherein the NaOH solution is a solution formed by dissolving 17.0g of NaOH in 30 mL deionized water;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and reacting for 12 hours at the temperature of 1 ℃ per minute to 200 ℃;
(1.3) cooling to room temperature, centrifuging, washing with water to ph=7, drying at 120 ℃ for 5 hours, placing in a muffle furnace, heating to 600 ℃ at 1 ℃/min, and air-roasting for 1 hour to obtain the carrier;
(2) Load metal:
(2.1) adding 2.01 gCu (NO 3)2·3H2 O into 5.0 (mL) acetone, stirring at room temperature until the solution is dissolved to obtain a metal salt solution;
(2.2) adding the carrier obtained in the step (1) into the metal salt solution, and stirring until the acetone is completely volatilized;
(2.3) heating to 600 ℃ in a muffle furnace at a heating rate of 1 ℃/min, and roasting with air for 1h to obtain the catalyst.
Evaluation of catalytic Effect of catalyst
A method for preparing glycine methyl ester and glycine from methyl glycolate comprises the following steps: filling a catalyst into a fixed bed reactor, reducing for 4 hours at 300 ℃ under normal pressure in a hydrogen atmosphere, regulating the flow rate of the hydrogen to 30mL/min, then adjusting the reaction temperature, pressurizing the reaction temperature to the reaction pressure by using nitrogen, and switching the reaction raw material into a reaction raw material feed; the product from the reactor enters a high-pressure separator after being cooled by a condenser, the liquid product enters a normal-pressure separator under the control of a liquid level meter, and tail gas is discharged after being converged into an ammonia absorption tower; wherein the reaction temperature is 150-320 ℃, the reaction pressure is 0.1-25.0MPa, the mass airspeed of the methyl glycolate is 0.05-4h -1, and the molar ratio of liquid ammonia to the methyl glycolate is 20-40:1;
The reaction conditions and results for the catalysts provided in the different examples are shown in Table 1;
TABLE 1 reaction conditions and results for different catalysts
Wherein the total selectivity of the amide is the sum of the selectivity of methyl glycine, methyl diglycolate and methyl triglycinate.
Second, stability detection
The catalyst of example 1 was reacted according to the above-described reaction procedure for evaluating the catalytic effect, and the reaction effect thereof at different reaction times was examined, as shown in Table 2; wherein the reaction temperature is 280 ℃, the reaction pressure is 10MPa, the mass airspeed of the methyl glycolate is 0.2h -1, and the molar ratio of liquid ammonia to the methyl glycolate is 30:1;
table 2 stability evaluation results
。

Claims (10)

1. A catalyst for preparing methyl glycine and glycine from methyl glycolate is characterized in that: the catalyst is a supported metal catalyst and consists of a catalyst carrier and metal supported on the carrier, wherein the metal is at least one of Co, ir, pd, ni, ru, cu, and the carrier is at least one of SiO 2、Al2O3、CeO2、ZrO2、TiO2; the weight ratio of the metal to the carrier is 0.01-35%.
2. The catalyst for preparing methyl glycine and glycine from methyl glycolate according to claim 1, wherein: the carrier is at least one of CeO 2、ZrO2、TiO2.
3. The catalyst for preparing glycine methyl ester and glycine from methyl glycolate according to claim 2, characterized in that: the weight ratio of the metal to the carrier is 0.03-30%.
4. The method for preparing glycine methyl ester and glycine catalyst from methyl glycolate according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) Preparing a carrier:
(1.1) mixing a solution of a carrier precursor with an alkaline solution, and stirring to obtain a suspension;
(1.2) transferring the suspension into a hydrothermal reaction kettle, sealing, and heating to 80-200 ℃ for reaction for 12-30h;
(1.3) cooling to room temperature, centrifuging, washing with water, drying, and roasting to obtain the carrier;
(2) Load metal:
(2.1) adding metal salt corresponding to the metal into a solvent, and stirring at room temperature until the metal salt is dissolved to obtain a metal salt solution;
(2.2) adding a carrier to the metal salt solution, and stirring until the solvent is completely volatilized;
(2.3) roasting to obtain the catalyst.
5. The method for preparing glycine methyl ester and glycine catalyst from methyl glycolate according to claim 4, wherein the method comprises the following steps: when the carrier is SiO 2, the corresponding carrier precursor is silicate; when the carrier is Al 2O3、CeO2、ZrO2、TiO2, the corresponding carrier precursor is a soluble metal salt corresponding to the metal contained in the carrier.
6. The method for preparing glycine methyl ester and glycine catalyst from methyl glycolate according to claim 5, wherein the method comprises the following steps: the soluble metal salt corresponding to the metal contained in the carrier is any one of nitrate, acetate, carbonate, phosphate and chloride; the alkaline solution is any one of ammonia water, sodium hydroxide and potassium hydroxide; the molar ratio of the carrier precursor to the alkaline substance in the alkaline solution is (0.01-1): (1-100).
7. The method for preparing glycine methyl ester and glycine catalyst from methyl glycolate according to claim 6, wherein the method comprises the following steps: in the step (2), the metal salt corresponding to the metal is acetate, chloride or nitrate thereof, and the solvent is acetone or ethanol.
8. The method for preparing glycine methyl ester and glycine catalyst from methyl glycolate according to claim 7, wherein the method comprises the following steps: the drying condition is that the drying is carried out for 5-20 hours at 60-120 ℃; the roasting condition is that roasting is carried out for 1-10h under the air atmosphere and the temperature is raised to 300-600 ℃.
9. A method for preparing glycine methyl ester and glycine from methyl glycolate, which is characterized by comprising the following steps: the method comprises the following steps: filling a catalyst into a fixed bed reactor, reducing the catalyst in a hydrogen atmosphere, adjusting the reaction temperature, and then pressurizing the reaction temperature to the reaction pressure by using nitrogen; methyl glycolate and liquid ammonia are mixed and then enter a preheater, and after preheating, the mixture is introduced into a reactor for reaction; wherein the reaction temperature is 150-320 ℃, the reaction pressure is 0.1-25.0MPa, and the catalyst is the catalyst of claim 1.
10. The method for preparing glycine methyl ester and glycine from methyl glycolate according to claim 9, wherein: the mass airspeed of the methyl glycolate is 0.05-4h -1, and the molar ratio of the liquid ammonia to the methyl glycolate is 20-40:1; the reduction condition is that the reduction is carried out for 3-4 hours under normal pressure and at 200-300 ℃, and the flow rate of hydrogen is 30-100mL/min.
CN202410213429.2A 2024-02-27 2024-02-27 Catalyst for preparing methyl glycine and glycine from methyl glycolate, and preparation method and application thereof Pending CN118162134A (en)

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CN202410213429.2A CN118162134A (en) 2024-02-27 2024-02-27 Catalyst for preparing methyl glycine and glycine from methyl glycolate, and preparation method and application thereof

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