CN114805132A - Method for preparing methyl carbamate - Google Patents
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- CN114805132A CN114805132A CN202210371163.5A CN202210371163A CN114805132A CN 114805132 A CN114805132 A CN 114805132A CN 202210371163 A CN202210371163 A CN 202210371163A CN 114805132 A CN114805132 A CN 114805132A
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- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 67
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 120
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004202 carbamide Substances 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 239000000376 reactant Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- -1 compound methyl carbamate Chemical class 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 241000275031 Nica Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 150000005677 organic carbonates Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 229960003965 antiepileptics Drugs 0.000 description 1
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NYXHSRNBKJIQQG-UHFFFAOYSA-N methyl n-methylcarbamate Chemical compound CNC(=O)OC NYXHSRNBKJIQQG-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003158 myorelaxant agent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/08—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing methyl carbamate by a urea alcoholysis method, which comprises the steps of adding methanol and urea into a heating magnetic high-pressure reaction kettle, stirring for 20 min at 30 ℃ to fully mix the methanol and the urea, then adding catalyst metal doped fluorhydroxyapatite with the structure of MCa 9 (PO 4 ) 6 F 2 Introduction of CO 2 Thirdly, after replacing the air in the kettle, CO in the reaction kettle 2 The pressure of the catalyst is 0.6 MPa, the reaction is carried out for 2 to 10 hours at the temperature of between 120 and 170 ℃, and the catalyst MCa 9 (PO 4 ) 6 F 2 The mass ratio of the urea to the total mass of the reactants urea and methanol is 1-5: 100, and the molar ratio of the methanol to the urea is 15:1; cooling the reaction system to room temperature, filtering to remove the catalystAnd (4) carrying out rotary evaporation on the solvent to obtain the target methyl carbamate. The selectivity of the obtained methyl carbamate can reach 98.9 percent at most, and the maximum yield of the methyl carbamate can reach 98.8 percent. The method has the characteristics of simple preparation process, mild reaction conditions, high yield of target products and the like, and is a clean preparation process of methyl carbamate.
Description
Technical Field
The invention belongs to the technical field of green synthesis of fine chemical engineering, and relates to a method for preparing methyl carbamate by a urea alcoholysis method.
Background
Methyl Carbamate (MC) with molecular formula of NH 2 COOCH 3 Is one of the simplest carbamates. The methyl carbamate is an ideal mothproofing agent for replacing camphor, and has the advantages of no smell, moderate volatility, low toxicity, good mothproofing effect and the like. Are also commonly used as other insecticides and fungicides. Methyl carbamate has long been used as a sedative drug in medicine, and in addition, it is also used as an anti-inflammatory agent, a muscle relaxant, an analgesic, an antiepileptic drug. In addition, the synthesis of isocyanate by cracking methyl carbamate is one of the main synthesis methods replacing phosgene method, industrial production is put into use in developed countries, and the demand of methyl carbamate is increased year by year as one of the most important raw materials of the method.
The method for synthesizing methyl carbamate mainly comprises a phosgene method, an organic carbonate ammonolysis method, a carbonylation method and a urea alcoholysis method. The phosgene method uses phosgene as a raw material and obtains methyl carbamate through alcoholysis and aminolysis, and the method has high production cost and serious environmental pollution. Therefore, the production of methyl carbamate by non-phosgene process has become a hot point of research. The organic carbonate method is a method of synthesizing methyl carbamate from an organic carbonate and an amine as raw materials, and has low conversion rate and yield, many by-products, and a long reaction time (reference, industrial catalysis, 2005, 13 (11): 30-33). The carbonylation method mainly refers to a reaction taking carbonyl source and organic amine as raw materials, and the reaction has the disadvantages of complex reaction mechanism, high toxicity of CO in the raw materials, easy explosion and low utilization rate (reference, modern chemical industry, 2009, 66 (29): 11-18).
At present, the application of the methyl carbamate in general materials is greatly limited due to high price and low yield of the methyl carbamate, so that the development of an effective catalyst for the process for synthesizing the methyl carbamate by the urea alcoholysis method has important research value. The method is characterized in that the requirements of the society on environmental protection are improved and green chemistry is developed, and the urea and the methanol are used as production raw materials, so that the method has the advantages of wide raw material sources, low raw material cost, simple reaction process, short flow and obvious economic benefit.
Zhang Mei Wen et al disclose a preparation method of methyl carbamate, under the conditions of reaction temperature of 100-180 ℃, reaction pressure of 0.1-1.5 MPa and reaction time of 0.5-10 h, ammonia gas and methanol are separated from ammonia-methanol mixed steam released in the reaction process through a rectifying tower, and the yield of methyl carbamate can reach 91% at most. However, in this reaction, methanol is continuously carried out of the reaction system, and the amount of raw materials and energy consumption are large (reference, CN 1683326). Dun friend et al disclose a catalyst for alkyl carbamate synthesis, wherein the reaction temperature is 160 ℃, by-products such as dimethyl carbonate and methyl methylcarbamate are formed during the reaction, and the problems of low yield of methyl carbamate and difficult separation of the by-products exist (reference, CN 101518729 a).
Since the beginning of the 21 st century, methyl carbamate was produced by a urea medium-pressure homogeneous catalysis method which is completed by the cooperation of China Petroleum university and Kangrui petrochemical industry Limited liability company in Shandong-Ying City of east China, and a 500 t/year production device was built and put into production smoothly in 2004. Plum-duckweed and the like catalyze urea to carry out alcoholysis to synthesize methyl carbamate by taking ZnO-KOH as a catalyst, wherein the molar ratio of the urea to the methanol is 1: the yield of methyl carbamate reaches 85% under the conditions of 60 hours, 8 hours and 185 ℃ (reference, fine chemical engineering and catalysis, 2006, 14, 47-50). The effect of four organometallic catalysts on this reaction was examined in Jianfeng et al [ reference. Industrial & Engineering Chemistry Research, 2013, 52(12):4408-4413] to find that the yield of methyl carbamate was 83.7% under the reaction conditions of methanol to urea to methanol molar ratio of 2:3, 160 ℃ and 6 h.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing methyl carbamate by a urea alcoholysis method.
The invention provides a method for preparing methyl carbamate by a urea alcoholysis method, which comprises the following steps and conditions:
(1) adding methanol and urea into a high-pressure reaction kettle with a magnetic stirrer and a heating temperature control system, stirring at 30 ℃ for 20 min to fully mix, and then adding catalyst XCa 9 (PO 4 ) 6 F 2 Introduction of CO 2 Thirdly, after replacing the air in the kettle, the air is in the reaction kettleCO 2 The pressure of the reaction is 0.6 MPa, the reaction is carried out for 2 to 10 hours at the temperature of between 120 and 170 ℃, and the catalyst XCa 9 (PO 4 ) 6 F 2 The mass ratio of the urea to the total mass of the reactants urea and methanol is 1-5: 100, and the molar ratio of the methanol to the urea is 15:1;
(2) and cooling the reaction system to room temperature, filtering to remove the catalyst, and performing rotary evaporation to obtain the target methyl carbamate.
The raw materials are that methanol and urea are analytically pure, and the adding proportion of the methanol and the urea is 10:1 to 20: 1; preferably 10: 1-15: 1;
the catalyst selected was XCa 9 (PO4) 6 F 2 Wherein M can be Zn, Cu, Ni, Mn, Mg, Fe transition metal; optimized to Zn, Cu, Ni;
the catalyst XCa 9 (PO 4 ) 6 F 2 The added mass is that the total mass of the reactants urea and methanol is 1-20: 100; preferably 1-5: 100.
Said first CO 2 The introduction times are 1-4 times; preferably 3 to 4 times.
The second CO introduction 2 Adjusting the reaction pressure to be 0.5-4 MPa, the reaction temperature to be 80-180 ℃, and the reaction time to be 0.5-10 h; wherein the reaction pressure is preferably 1-2 MPa, the reaction temperature is preferably 120-170 ℃, and the reaction time is preferably 2-10 h.
Compared with the prior art, the invention has the following beneficial effects
The invention provides a method for preparing methyl carbamate by a urea alcoholysis method, which takes urea and methanol as raw materials and XCa 9 (PO 4 ) 6 F 2 The reaction medium was methanol as catalyst, giving a selectivity of 98.9% for methyl carbamate and a maximum yield of 98.8% for methyl carbamate. The production method of methyl carbamate has the characteristics of simple preparation process, mild reaction conditions, high yield of target products and the like, and is a clean preparation process of methyl carbamate.
Detailed Description
Method for testing yield of methyl carbamate as target: the content of methyl carbamate was analyzed by gas chromatography. The chromatographic analysis conditions were: gas chromatograph Agilent GC6890, analysis conditions: HP-5 capillary column, FID detector, injection port temperature of 240 deg.C, detector temperature of 280 deg.C. The sample size was 1.0. mu.L.
Example 1: (1) adding methanol and urea into a high-pressure reaction kettle with a magnetic stirrer and a heating temperature control system, stirring for 20 min at 30 ℃ to fully mix, and then adding a catalyst ZnCa 9 (PO 4 ) 6 F 2 Introduction of CO 2 Thirdly, after replacing the air in the kettle, CO in the reaction kettle 2 The pressure of the catalyst is 0.6 MPa, the reaction is carried out for 6 hours at the temperature of 160 ℃, and the catalyst ZnCa 9 (PO 4 ) 6 F 2 The mass ratio of (a) to the total mass of the reactants urea and methanol is 4: 100, the molar ratio of methanol to urea is 15:1; the specific addition amount is as follows: 1.0 g of urea, 10 mL of methanol and ZnCa catalyst 9 (PO 4 ) 6 F 2 0.72 g；
(2) And cooling the reaction system to room temperature, filtering to remove the catalyst, and performing rotary evaporation to obtain the target product methyl carbamate. The results are shown in Table 1.
Example 2: the step (1) is to react for 2 hours at the temperature of 140 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 3: the step (1) is to react for 4 hours at the temperature of 140 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 4: the step (1) is carried out for 8 hours at the temperature of 140 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 5: the step (1) is to react for 10 hours at the temperature of 140 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 6: the step (1) is to react for 6 hours at the temperature of 120 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 7: the step (1) is carried out for 6 hours at the temperature of 130 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 8: the step (1) is to react for 6 hours at the temperature of 150 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 9: the step (1) is carried out for 6 hours at the temperature of 160 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 10: the step (1) is carried out for 6 hours at the temperature of 170 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 11: the catalyst ZnCa is obtained in the step (1) 9 (PO 4 ) 6 F 2 The mass ratio of the mass of (a) to the mass of the reactants urea and methanol is 1: 100, then adding catalyst ZnCa 9 (PO 4 ) 6 F 2 Reacting for 6 hours at the temperature of 160 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 12: the catalyst ZnCa is obtained in the step (1) 9 (PO 4 ) 6 F 2 The mass ratio of the reactants urea and methanol is 2: 100, then adding catalyst ZnCa 9 (PO 4 ) 6 F 2 Reacting for 6 hours at the temperature of 160 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 13: the catalyst ZnCa is obtained in the step (1) 9 (PO 4 ) 6 F 2 The mass ratio of the mass of (a) to the mass of the reactants urea and methanol is 3: 100, then adding catalyst ZnCa 9 (PO 4 ) 6 F 2 Reacting for 6 hours at the temperature of 160 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 14: the catalyst ZnCa is obtained in the step (1) 9 (PO 4 ) 6 F 2 The mass ratio of the mass of (a) to the mass of the reactants urea and methanol is 5:100, then adding catalyst ZnCa 9 (PO 4 ) 6 F 2 Reacting for 6 hours at the temperature of 160 ℃; the rest of the process was the same as in example 1. The results are shown in Table 1.
Example 15: (1) with magnetic stirringAdding methanol and urea into a high-pressure reaction kettle of a heating temperature control system, stirring at 30 deg.C for 20 min for mixing, and adding CuCa catalyst 9 (PO 4 ) 6 F 2 Introduction of CO 2 Thirdly, after replacing the air in the kettle, CO in the reaction kettle 2 The pressure of the catalyst is 0.6 MPa, the reaction is carried out for 6 hours at the temperature of 160 ℃, and the catalyst ZnCa 9 (PO 4 ) 6 F 2 The mass ratio of (a) to the total mass of the reactants urea and methanol is 4: 100, the molar ratio of methanol to urea is 15:1; the specific addition amount is as follows: 1.0 g of urea, 10 mL of methanol and CuCa catalyst 9 (PO 4 ) 6 F 2 0.72 g；
(2) And cooling the reaction system to room temperature, filtering to remove the catalyst, and performing rotary evaporation to obtain the target product methyl carbamate.
The content of the obtained methyl carbamate as a target substance was analyzed by gas chromatography. The chromatographic analysis conditions were: gas chromatograph Agilent GC6890, analysis conditions: HP-5 capillary column, FID detector, injection port temperature of 240 deg.C, detector temperature of 280 deg.C. The amount of the sample was 1.0. mu.L. The results are shown in Table 2.
Example 16: the step (1) is to react for 4 hours at the temperature of 120 ℃; the rest of the process was the same as in example 15. The results are shown in Table 2.
Example 17: the step (1) is to react for 4 hours at the temperature of 140 ℃; the rest of the process was the same as in example 15. The results are shown in Table 2.
Example 18: the step (1) is carried out for 6 hours at the temperature of 160 ℃; the rest of the process was the same as in example 15. The results are shown in Table 2.
Example 19: (1) adding methanol and urea into a high-pressure reaction kettle with a magnetic stirrer and a heating temperature control system, stirring at 30 ℃ for 20 min to fully mix, and then adding a catalyst NiCa 9 (PO 4 ) 6 F 2 Introduction of CO 2 Thirdly, after replacing the air in the kettle, CO in the reaction kettle 2 The pressure of the catalyst is 0.6 MPa, the reaction is carried out for 6 hours at the temperature of 160 ℃, and the catalyst NiCa 9 (PO 4 ) 6 F 2 The mass ratio of (a) to the total mass of the reactants urea and methanol is 4: 100, the molar ratio of methanol to urea is 15:1; the specific addition amount is as follows: 1.0 g of urea, 10 mL of methanol and NiCa catalyst 9 (PO 4 ) 6 F 2 0.72 g；
(2) And cooling the reaction system to room temperature, filtering to remove the catalyst, and performing rotary evaporation to obtain the target product methyl carbamate.
The content of the obtained methyl carbamate as a target substance was analyzed by gas chromatography. The chromatographic analysis conditions were: gas chromatograph Agilent GC6890, analysis conditions: HP-5 capillary column, FID detector, injection port temperature of 240 deg.C, detector temperature of 280 deg.C. The amount of the sample was 1.0. mu.L. The results are shown in Table 3.
Example 20: the step (1) is to react for 4 hours at the temperature of 120 ℃; the rest of the process was the same as in example 19. The results are shown in Table 3.
Example 21: the step (1) is to react for 4 hours at the temperature of 140 ℃; the rest of the process was the same as in example 19. The results are shown in Table 3.
Example 22: the step (1) is carried out for 6 h at the temperature of 160 ℃; the rest of the process was the same as in example 19. The results are shown in Table 3.
The data in Table 1 show that the process for the preparation of methyl carbamate by the urea alcoholysis process of the present invention, for example 1, has a urea conversion of 99.8%, a selectivity for methyl carbamate of 98.9% and a maximum yield of methyl carbamate of 98.8%.
The data in Table 2 show that the process for the preparation of methyl carbamate by the urea alcoholysis process of the present invention, for example 15, has a urea conversion of 86.8%, a selectivity for methyl carbamate of 83.4% and a maximum yield of methyl carbamate of 72.4%.
The data in Table 3 show that the process for the preparation of methyl carbamate by the urea alcoholysis process of the present invention, for example 19, has a urea conversion of 75.5%, a selectivity for methyl carbamate of 80.8% and a maximum yield of methyl carbamate of 61.0%.
TABLE 1 ZnCa 9 (PO 4 ) 6 F 2 Is the influence of the catalyst and the reaction conditions on the product
| Examples | Urea conversion (%) | Selectivity to methyl carbamate (%) | Methyl carbamate yield (%) |
| 1 | 99.8 | 98.8 | 98.9 |
| 2 | 60.1 | 58.4 | 97.2 |
| 3 | 84.4 | 80.1 | 94.9 |
| 4 | 99.8 | 82.2 | 82.4 |
| 5 | 100 | 78.3 | 78.3 |
| 6 | 70.6 | 65.3 | 92.5 |
| 7 | 75.9 | 72.4 | 95.4 |
| 8 | 91.4 | 88.3 | 96.6 |
| 9 | 99.6 | 97.2 | 97.5 |
| 10 | 100 | 90.2 | 90.2 |
| 11 | 76.3 | 70.2 | 92.0 |
| 12 | 88.2 | 82.4 | 93.4 |
| 13 | 94.3 | 92.1 | 97.6 |
| 14 | 99.8 | 88.9 | 89.1 |
TABLE 2CuCa 9 (PO 4 ) 6 F 2 Is the influence of the catalyst and the reaction conditions on the product
| Examples | Urea conversion (%) | Selectivity to methyl carbamate (%) | Methyl carbamate yield (%) |
| 15 | 86.8 | 83.4 | 72.4 |
| 16 | 84.4 | 80.1 | 67.6 |
| 17 | 85.2 | 82.4 | 70.2 |
| 18 | 86.8 | 82.8 | 71.2 |
TABLE 3NiCa 9 (PO 4 ) 6 F 2 Is the influence of the catalyst and the reaction conditions on the product
| Examples | Urea conversion (%) | Selectivity to methyl carbamate (%) | Methyl carbamate yield (%) |
| 19 | 75.5 | 80.8 | 61.0 |
| 20 | 60.1 | 58.4 | 35.1 |
| 21 | 70.3 | 80.5 | 56.6 |
| 22 | 70.6 | 81.2 | 57.3 |
Claims (9)
1. A process for the preparation of methyl carbamate, characterized by the following steps and conditions:
(1) adding methanol and urea into a high-pressure reaction kettle with a magnetic stirrer and a heating temperature control system, stirring at 30 ℃ for 20 min to fully mix, and then adding catalyst XCa 9 (PO 4 ) 6 F 2 Introduction of CO 2 After replacing the air in the kettle, continuously introducing CO 2 Making the system pressure constant, regulating reaction temp. and reaction time, catalyst XCa 9 (PO 4 ) 6 F 2 The mass ratio of the urea to the total mass of the reactants urea and methanol is 1-5: 100, and the molar ratio of the methanol to the urea is 15:1;
(2) and cooling the reaction system to room temperature, filtering to remove the catalyst, and performing rotary evaporation to obtain the target methyl carbamate.
2. The method for preparing methyl carbamate according to claim 1, wherein the reaction kettle is made of stainless steel, can bear the pressure of 5MPa and can resist the high temperature of 200 ℃.
3. The method of claim 1, wherein the raw materials of methanol and urea are analytically pure, and the ratio of methanol to urea is 5:1 to 15: 1.
4. The process of claim 1, wherein the catalyst selected is XCa 9 (PO 4 ) 6 F 2 Wherein X may be any of Zn, Cu,ni, Mn, Mg, Fe and the like.
5. The process of claim 1, wherein the catalyst XCa is a catalyst 9 (PO 4 ) 6 F 2 The mass ratio of the added urea and methanol is 1-5: 100.
6. The method as claimed in claim 1, wherein the CO is introduced from the gas inlet for the first time 2 With the gas outlet of the system in an open state, CO 2 And discontinuously introducing, namely adopting an intermittent method, wherein the introduction times are 1-4 times, and the gas outlet is closed after air in the kettle is completely replaced according to the dosage of the reaction raw materials.
7. The method as claimed in claim 1, wherein the CO is introduced for the second time 2 In order to adjust the reaction pressure of the reaction system, the reaction pressure is controlled to be 0.5-4 MPa, the temperature required by the reaction is controlled to be 80-180 ℃, and the reaction time is 0.5-10 h.
8. The process for producing methyl carbamate according to claim 1, wherein the methyl carbamate as the target is purified by a rotary evaporation apparatus.
9. The method according to claim 1, wherein the target compound methyl carbamate is used in the fields of medicine and organic synthesis.
Priority Applications (1)
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| CN115382583A (en) * | 2022-09-28 | 2022-11-25 | 长春工业大学 | Preparation and application of high-efficiency catalytic water absorption material |
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| CN105777583A (en) * | 2016-05-07 | 2016-07-20 | 长春工业大学 | Method for preparing methyl carbamate by urea methanolysis method |
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| CN105777583A (en) * | 2016-05-07 | 2016-07-20 | 长春工业大学 | Method for preparing methyl carbamate by urea methanolysis method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382583A (en) * | 2022-09-28 | 2022-11-25 | 长春工业大学 | Preparation and application of high-efficiency catalytic water absorption material |
| CN115382583B (en) * | 2022-09-28 | 2024-05-03 | 长春工业大学 | Preparation and application of efficient catalytic water absorbing material |
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