CN114621108B - Method for preparing glycine from glyoxylic acid - Google Patents
Method for preparing glycine from glyoxylic acid Download PDFInfo
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- CN114621108B CN114621108B CN202011445297.4A CN202011445297A CN114621108B CN 114621108 B CN114621108 B CN 114621108B CN 202011445297 A CN202011445297 A CN 202011445297A CN 114621108 B CN114621108 B CN 114621108B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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Abstract
The application discloses a method for preparing glycine by glyoxylic acid. The method comprises the following steps: adding material containing glyoxylic acid and solvent into NH 3 、H 2 Under the existing condition, the glycine is contacted with a catalyst and an additive to react to obtain glycine; wherein the catalyst is a supported metal catalyst; the supported metal catalyst comprises a metal and a carrier; the metal is supported on a carrier; the metal is at least one of Ni and Ru; the carrier is a carrier I and/or a carrier II; the carrier I is at least one selected from activated carbon, mesoporous carbon and carbon nano tubes; the carrier II is selected from TiO 2 、ZrO 2 At least one of; the additive is organic amine. The method has the advantages of green and environment-friendly raw materials, low cost, simple process, high conversion rate, high product selectivity and the like.
Description
Technical Field
The application relates to a method for preparing glycine from glyoxylic acid, belonging to the field of organic chemical industry.
Background
Glycine, also known as glycine, is the amino acid with the simplest structure, is an important intermediate for organic synthesis, and is widely applied to the fields of pesticides, medicines, feeds, foods and the like. Glycine is used as an antioxidant and a preservative of medicines, feeds and foods, and also used for treating myasthenia gravis, progressive muscular atrophy, chronic enteritis, hyperacidity and hyperprolinemia in children, is used for synthesizing medicines such as vitamin B6, threonine, cephalosporin, thiamphenicol, delapril hydrochloride, oxalglycine aspirin calcium, paracetamol glycinate, glycine acetylcalcium salicylate, reserpine and the like, and pesticides such as insecticide pyrethroid, bactericide iprodione, herbicide glyphosate, plant growth regulator glyphosine and the like.
The conventional preparation method of glycine comprises the following steps: (1) The method comprises the following steps of (Strecker) synthesizing aminoacetonitrile by using formaldehyde, hydrocyanic acid and ammonia as raw materials and then hydrolyzing to prepare glycine; (2) The Bucherer method uses trioxymethylene, ammonium carbonate, sodium cyanide and the like as raw materials to synthesize glycine; (3) The monochloroacetic acid ammoniation method uses ammonia water and monochloroacetic acid as raw materials to synthesize glycine. The preparation of glycine by the Schterek method and the Bucherer method uses highly toxic raw materials such as hydrocyanic acid, sodium cyanide and the like, and has large environmental impact and poor safety. The selectivity of the glycine prepared by the monochloroacetic acid ammonification method is not easy to control, byproducts such as iminodiacetic acid, nitrilotriacetic acid and the like are easy to generate, the selectivity of the glycine is low, the consumption of raw materials is high, and chlorine is used as the raw material for producing the monochloroacetic acid, so that the environmental impact is large and the safety is poor.
Disclosure of Invention
In order to solve the problems of high toxicity, large environmental influence, poor safety, high raw material consumption, poor selectivity and the like of the existing raw materials for preparing the glycine, the application provides the method for preparing the glycine from the glyoxylic acid, and the method has the advantages of green and environment-friendly raw materials, low cost, simple process, high conversion rate, high product selectivity and the like.
The technical scheme for preparing the glycine from the glyoxylic acid comprises the following steps: adding material containing glyoxylic acid and solvent into NH 3 、H 2 In the presence of catalyst and additive, reacting to obtain glycine.
According to the invention, catalysts and additives are of great importance. Without catalyst, without additive or with low catalyst activity, the glyoxylic acid conversion is very low. When the activity and the selectivity of the catalyst and the additive are high, the high conversion rate of the glyoxylic acid and the high selectivity of the glycine can be obtained.
According to the invention, the catalyst is a supported metal catalyst;
the supported metal catalyst comprises a metal and a carrier;
the metal is supported on a carrier;
the metal is at least one of Ni and Ru;
the carrier is a carrier I and/or a carrier II;
the carrier I is at least one selected from activated carbon, mesoporous carbon and carbon nano tubes;
the carrier II is selected from TiO 2 、ZrO 2 At least one of;
the additive is organic amine.
Alternatively, the method for preparing the supported metal catalyst using the carrier I comprises:
mixing and stirring A solution containing soluble salt of the metal and a carrier I, drying, roasting in an inactive atmosphere, roasting the obtained product and KBH containing KOH 4 Mixing and stirring the aqueous solution B to obtain the supported metal catalyst;
optionally, the inert atmosphere is selected from at least one of nitrogen, argon;
optionally, in the solution of the soluble salt of the metal, the mass concentration of the soluble salt of the metal is 5-20%;
the mass ratio of the solution of the soluble salt of the metal to the carrier I is 1:1-2:1;
optionally, the mass concentration of the soluble salt of the metal is independently selected from any value of 5%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20% or a range value between any two;
alternatively, the KBH containing KOH 4 In the aqueous solution, the mass concentration of KOH is 5 to 10 percent, and KBH 4 The mass concentration of (A) is 10-20%;
the roasted product and KBH containing KOH 4 The mass ratio of the aqueous solution is 1:1-1:3;
optionally, the time of the mixing stirring A and the mixing stirring B is independently 4 to 6 hours;
the drying temperature is 50-100 ℃, and the drying time is 2-6 h;
the roasting temperature is 300-500 ℃, and the roasting time is 2-4 h;
optionally, the temperature of the drying is independently selected from any value of 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or a range value between any two;
optionally, the temperature of the firing is independently selected from any of 300 ℃, 340 ℃, 380 ℃, 400 ℃, 440 ℃, 450 ℃, 460 ℃, 480 ℃, 500 ℃ or a range value between any two.
Alternatively, the method for preparing the supported metal catalyst using the carrier II comprises:
mixing the solution containing soluble salt of the metal and the precursor of the carrier II, drying, and reacting in H 2 Roasting to obtain the supported metal catalyst;
optionally, the precursor of the carrier II is selected from a compound represented by formula (a):
wherein M is Ti or Zr;
r is C1-C4 alkyl;
optionally, the precursor of the carrier II is selected from at least one of tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetraethyl zirconate, tetrapropyl zirconate and tetrabutyl zirconate;
optionally, in the solution of the soluble salt of the metal, the mass concentration of the soluble salt of the metal is 5-20%;
the mass ratio of the solution of the soluble salt of the metal to the precursor of the carrier II is 1:1-1:5;
optionally, the mixing and stirring time is 4-6 h;
the drying temperature is 50-100 ℃, and the drying time is 2-6 h;
the roasting temperature is 500-700 ℃, and the roasting time is 3-5 h;
optionally, the temperature of the drying is independently selected from any value of 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or a range value between any two;
optionally, the temperature of the firing is independently selected from any of 500 ℃, 540 ℃, 580 ℃, 600 ℃, 640 ℃, 650 ℃, 660 ℃, 680 ℃, 700 ℃, or a range value between any two.
Optionally, the organic amine is at least one of n-hexylamine, n-pentylamine, and n-butylamine.
Optionally, the solvent is at least one of methanol, ethanol, isopropanol, butanol.
OptionallyThe mass concentration of the glyoxylic acid in a reaction system is 10-50%, wherein the reaction system comprises the glyoxylic acid, a solvent and NH 3 Catalysts and additives.
Optionally, the mass concentration of the glyoxylic acid in the reaction system is independently selected from any value of 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or a range between any two.
Optionally, the amount of the catalyst is 0.5-2.0% of the mass of the glyoxylic acid.
Optionally, the amount of the catalyst is independently selected from any value of 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2% or a range between any two of the above.
Optionally, the mass ratio of the additive to the glyoxylic acid is 1:1-2:1.
Alternatively, the NH 3 The mass ratio of the glyoxylic acid to the glyoxylic acid is 1:2-2:1.
Alternatively, the reaction conditions are:
H 2 the pressure is 1-3 MPa;
the reaction temperature is 80-150 ℃, and the reaction time is 3-6 h.
Optionally, the reaction pressure is independently selected from any of 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, or a range between any two.
Optionally, the reaction temperature is independently selected from any value of 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or a range value between any two.
Optionally, the reaction time is independently selected from any of 3h, 4h, 5h, 6h, or a range of values between any two.
In the present application, C1-C4 refers to the number of carbon atoms that a compound or group contains.
In the present application, alkyl refers to a group formed by the loss of any one hydrogen atom from the molecule of an alkane compound, including straight-chain or branched alkanes. For example, the C1-C4 alkyl group can be methyl, ethyl, propyl, butyl, isopropyl, and the like.
The beneficial effects that this application can produce include:
the method for preparing glycine from glyoxylic acid solves the problems of high toxicity of raw materials, large environmental influence, poor safety, high raw material consumption, poor selectivity and the like in the prior glycine preparation, has the advantages of green and environment-friendly raw materials, low cost, simple process, high conversion rate, high product selectivity and the like, and has good industrial application prospect.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially unless otherwise specified, and the test methods were carried out by conventional methods.
The conversion, selectivity in the examples of the present application were calculated as follows:
example 1
20g of Ni (NO) with the mass percent concentration of 20 percent 3 ) 2 Mixing the water solution with 10g of activated carbon, stirring for 4h, drying at 100 ℃ for 2h 2 Roasting for 2h at 500 ℃ in the atmosphere. Taking 10g of the above-mentioned roasted product and 10g of KBH containing KOH 4 Mixing the aqueous solution with stirring for 6h, wherein the KBH contains KOH 4 The mass percentage of KOH in the aqueous solution is 10 percent, and KBH 4 The mass percentage of the active carbon supported Ni catalyst is 20 percent, the obtained mixture is filtered, and filter residues are washed by water to obtain the active carbon supported Ni catalyst which is marked as Ni/AC-B.
Example 2
Example 2 is similar to example 1 except that the fired product was not passed over KBH containing KOH 4 Aqueous solution treatment, used directly as catalyst, is noted as Ni/AC.
Example 3
10g of Ni (NO) with a concentration of 10% by mass 3 ) 2 Mixing the aqueous solution with 10g of mesoporous carbon, stirring for 6h, drying at 50 ℃ for 6h 2 Roasting at 300 deg.c for 4 hr. Taking 10g of the above-mentioned roasted product and 30g of KBH containing KOH 4 Mixing the aqueous solution with stirring for 4h, wherein the KBH contains KOH 4 The mass percentage of KOH in the aqueous solution is 5 percent, and KBH 4 The mass percentage of the catalyst is 10 percent, the obtained mixture is filtered, and filter residue is washed by water to obtain the mesoporous carbon supported Ni catalyst which is marked as Ni/MC-B.
Example 4
10g of RuCl with the concentration of 5 percent by mass 2 Mixing the aqueous solution and 10g of carbon nano tubes, stirring for 5h, drying at 80 ℃ for 4h 2 Roasting at 400 ℃ for 3h under the atmosphere. Taking 10g of the above-mentioned roasted product and 20g of KBH containing KOH 4 Mixing the aqueous solution with stirring for 5h, wherein the KBH contains KOH 4 The mass percentage of KOH in the aqueous solution is 8 percent, and KBH 4 The mass percentage of the catalyst is 15%, filtering the obtained mixture, and washing filter residues with water to obtain the carbon nano tube loaded Ru catalyst which is marked as Ru/CNT-B.
Example 5
10g of Ni (NO) with a concentration of 20% by mass 3 ) 2 Mixing the aqueous solution with 50g tetrabutyl titanate, stirring for 4h, drying at 100 deg.C for 2h 2 Roasting at 700 ℃ for 3h under the atmosphere to obtain TiO 2 Supported Ni catalyst, denoted Ni/TiO 2 -1。
Example 6
Example 6 is similar to example 5, except that the TiO was purchased directly in the commercial market 2 The carrier is prepared by the following specific steps: 10g of Ni (NO) with a concentration of 20% by mass 3 ) 2 Aqueous solution and 10g TiO 2 Mixing and stirring for 4h, drying at 100 deg.C for 2h 2 Roasting at 700 ℃ for 3h under the atmosphere to obtain TiO 2 Supported Ni catalyst, denoted Ni/TiO 2 -2。
Example 7
10g of NiCl with the mass percent concentration of 10 percent 2 The aqueous solution and 10g of tetraethyl zirconate are mixed and stirred for 6 hoursDrying at 50 ℃ for 6h 2 Roasting at 500 ℃ for 5h under atmosphere to obtain ZrO 2 Ni Supported catalysts, denoted Ni/ZrO 2 。
Example 8
10g of RuCl with a concentration of 5% by mass 2 The aqueous solution and 20g tetrapropyl titanate were mixed and stirred for 5h, dried at 80 ℃ for 5h 2 Roasting at 600 ℃ for 4h under atmosphere to obtain TiO 2 Supported Ru catalysts, denoted Ru/TiO 2 。
Example 9
Mixing 2g glyoxylic acid and 5g ethanol, adding 0.04g Ni/AC-B catalyst prepared in example 1, adding 3g n-hexylamine and 1g NH 3 Is charged with 2MPa H 2 Stirring, heating to 100 ℃, reacting for 6h, and carrying out qualitative and quantitative analysis on reaction products by gas chromatography-mass spectrometry, wherein the conversion rate of the glyoxylic acid is 99 percent, and the selectivity of the glycine is 99 percent.
Example 10
Example 10 is similar to example 9, except that: no n-hexylamine was added as an additive. As a result, the conversion rate of glyoxylic acid is 99 percent, and the selectivity of glycine is only 22 percent.
Examples 11 to 17
Examples 11 to 17 the reaction conditions were the same as in example 9, except that: the results are shown in table 1 using different catalysts.
Example 11 differs from example 9 in that: the catalyst was the catalyst prepared in example 2 without KBH 4 The treated activated carbon supported a Ni catalyst (noted Ni/AC).
Example 12 differs from example 9 in that: the catalyst was the mesoporous carbon supported Ni catalyst (noted Ni/MC-B) prepared in example 3.
Example 13 differs from example 9 in that: the catalyst was the carbon nanotube-supported Ru catalyst (noted Ru/CNT-B) prepared in example 4.
Example 14 differs from example 9 in that: the catalyst was TiO prepared in example 5 2 Supported Ni catalyst (denoted as Ni/TiO) 2 -1)
Example 15 differs from example 9 in that: the catalyst was that obtained in example 6TiO 2 Supported Ni catalyst (denoted as Ni/TiO) 2 -2)
Example 16 differs from example 9 in that: the catalyst was ZrO prepared in example 7 2 Supported Ni catalyst (denoted as Ni/ZrO) 2 )
Example 17 differs from example 9 in that: the catalyst was TiO prepared as in example 8 2 Supported Ru catalysts (noted Ru/TiO) 2 )
TABLE 1 catalytic Effect of different catalysts on the preparation of Glycine from glyoxylic acid
Example 11 use of an unbackh 4 The treated active carbon loaded Ni catalyst, glycine selectivity was only 68%. Comparison with the experimental results of example 9 shows that the catalyst preparation process has a great influence on the reaction result of glyoxylic acid to glycine. In examples 12 and 13, the mesoporous carbon supported Ni catalyst and the carbon nanotube supported Ru catalyst were used, respectively, and the glyoxylic acid conversion rate was 99% and the glycine selectivity was 95% or more.
Example 14 hydrolysis of Using tetrabutyltitanate and calcination of the resulting TiO 2 The prepared supported Ni catalyst has glyoxylate conversion rate up to 99% and glycine selectivity up to 95%. Example 15 use of commercially available TiO 2 The glycine selectivity of the prepared supported Ni catalyst is only 48%. A comparison of the results of examples 14 and 15 shows that the catalyst preparation process has a significant effect on the results of the reaction of glyoxylic acid to glycine. Examples 16 and 17 use respectively ZrO obtained by hydrolysis and calcination of tetraethyl zirconate 2 The prepared supported Ni catalyst and TiO obtained by hydrolyzing tetrapropyl titanate and roasting 2 The prepared supported Ru catalyst has glyoxylate conversion rate of 99 percent and glycine selectivity of over 96 percent.
Examples 18 to 25
Examples 18-25 investigated the effect of different conditions on the results of the Ni/AC-B catalyzed reaction of glyoxylic acid to glycine, and the specific procedure was similar to example 9, except that: solvent, catalyst amount, additive type and amount, substrate concentration, and H 2 The results are shown in Table 2, with the pressure, reaction temperature or reaction time varying. At NH 3 、H 2 Under the atmosphere, in solvents such as methanol, ethanol, isopropanol, butanol and the like, ni/AC-B is used as a catalyst, the dosage of the catalyst is 0.5-2.0 percent of the mass of glyoxylic acid, n-hexylamine, n-pentylamine, n-butylamine and the like are used as additives, the mass ratio of the additives to the glyoxylic acid is 1:1-2:1, the mass percent concentration of a glyoxylic acid reaction substrate is 10-50 percent, and NH is added 3 The mass ratio of the raw material to the glyoxylic acid is 1:2-2:1, the reaction temperature is 80-150 ℃, and H is 2 The pressure is 1-3 MPa, the reaction time is 3-6 h, the conversion rate of the glyoxylic acid can reach more than 95 percent, and the selectivity of the glycine can reach more than 90 percent.
TABLE 2 influence of reaction conditions on Ni/AC-B catalysis of glyoxylic acid to glycine
In the present application, the "substrate concentration" refers to the mass percentage concentration of glyoxylic acid in a reaction system consisting of glyoxylic acid, a solvent and NH 3 Catalyst and additive.
In summary, the present application is directed to NH 3 、H 2 Under the atmosphere, in a solvent such as methanol, ethanol, isopropanol, n-butanol and the like, in an additive such as n-hexylamine, n-pentylamine, n-butylamine and the like, activated carbon, mesoporous carbon, carbon nano tubes, tiO 2 、ZrO 2 Under the existence of Ni or Ru catalyst, the conversion rate of glyoxylic acid and the selectivity of glycine can reach 99%. The method has the advantages of green and environment-friendly raw materials, low cost, simple process, high conversion rate, high product selectivity and the like.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The method for preparing glycine by glyoxylic acid is characterized in that a material containing glyoxylic acid and a solvent is put into NH 3 、H 2 Under the existing condition, the glycine is contacted with a catalyst and an additive to react to obtain glycine;
wherein the catalyst is a supported metal catalyst;
the supported metal catalyst comprises a metal and a carrier;
the metal is supported on a carrier;
the metal is at least one of Ni and Ru;
the carrier is a carrier I and/or a carrier II;
the carrier I is at least one selected from activated carbon, mesoporous carbon and carbon nano tubes;
the carrier II is selected from TiO 2 、ZrO 2 At least one of;
the additive is organic amine;
the preparation method of the supported metal catalyst comprises the following steps:
mixing and stirring A solution containing soluble salt of the metal and a carrier I, drying, roasting in an inactive atmosphere, roasting the obtained product and KBH containing KOH 4 Mixing and stirring the aqueous solution B to obtain the supported metal catalyst; or mixing and stirring the solution containing the soluble salt of the metal and the precursor of the carrier II, drying and then adding the mixture into the carrier II 2 Roasting to obtain the supported metal catalyst;
the precursor of the carrier II is selected from a compound shown as a formula (a):
wherein M is Ti or Zr;
r is C1-C4 alkyl;
the organic amine is at least one of n-hexylamine, n-pentylamine and n-butylamine.
2. The method according to claim 1, wherein in the solution of the soluble salt of the metal, the mass concentration of the soluble salt of the metal is 5% -20%;
the mass ratio of the solution of the soluble salt of the metal to the carrier I is 1 to 1;
the KBH containing KOH 4 In the aqueous solution, the mass concentration of KOH is 5-10%, and KBH 4 The mass concentration of (A) is 10 to 20 percent;
the roasted product and KBH containing KOH 4 The mass ratio of the aqueous solution is 1 to 1.
3. The method according to claim 1, wherein the mixing and stirring A and the mixing and stirring B are independently carried out for 4 to 6 hours;
the drying temperature is 50 to 100 ℃, and the drying time is 2 to 6 hours;
the baking temperature is 300 to 500 ℃, and the baking time is 2 to 4 hours.
4. The method according to claim 1, wherein in the solution of the soluble salt of the metal, the mass concentration of the soluble salt of the metal is 5% -20%;
the mass ratio of the solution of the soluble salt of the metal to the precursor of the carrier II is 1 to 1;
the mixing and stirring time is 4 to 6 hours;
the drying temperature is 50 to 100 ℃, and the drying time is 2 to 6 hours;
the roasting temperature is 500 to 700 ℃, and the roasting time is 3 to 5 hours.
5. The method of claim 1,
the solvent is at least one of methanol, ethanol, isopropanol and butanol.
6. The method according to claim 1, wherein the mass concentration of the glyoxylic acid in a reaction system is 10 to 50 percent, wherein the reaction system comprises the glyoxylic acid, a solvent and NH 3 Catalysts and additives;
the dosage of the catalyst is 0.5 to 2.0 percent of the mass of the glyoxylic acid;
the mass ratio of the additive to the glyoxylic acid is 1 to 1;
the NH 3 The mass ratio of the raw materials to glyoxylic acid is 1 to 2;
said H 2 The pressure is 1 to 3MPa;
the reaction temperature is 80 to 150 ℃, and the reaction time is 3 to 6h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5990323A (en) * | 1998-10-23 | 1999-11-23 | Eastman Chemical Company | Preparation of amines |
| CN102019185A (en) * | 2009-09-16 | 2011-04-20 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in hydrocracking reaction of xylitol |
| CN110606806A (en) * | 2019-10-04 | 2019-12-24 | 重庆工商大学 | Method for synthesizing primary amine under catalysis of nano ruthenium |
| CN111116375A (en) * | 2019-12-13 | 2020-05-08 | 中国科学院广州能源研究所 | Method for preparing primary amine by catalyzing aldehyde ketone compound through reductive amination |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6624490B2 (en) * | 2015-07-17 | 2019-12-25 | 国立研究開発法人産業技術総合研究所 | Method for producing aromatic compound or furan derivative having methylamino group |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5990323A (en) * | 1998-10-23 | 1999-11-23 | Eastman Chemical Company | Preparation of amines |
| CN102019185A (en) * | 2009-09-16 | 2011-04-20 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in hydrocracking reaction of xylitol |
| CN110606806A (en) * | 2019-10-04 | 2019-12-24 | 重庆工商大学 | Method for synthesizing primary amine under catalysis of nano ruthenium |
| CN111116375A (en) * | 2019-12-13 | 2020-05-08 | 中国科学院广州能源研究所 | Method for preparing primary amine by catalyzing aldehyde ketone compound through reductive amination |
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