CN105777583A - Method for preparing methyl carbamate by urea methanolysis method - Google Patents
Method for preparing methyl carbamate by urea methanolysis method Download PDFInfo
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- CN105777583A CN105777583A CN201610295989.2A CN201610295989A CN105777583A CN 105777583 A CN105777583 A CN 105777583A CN 201610295989 A CN201610295989 A CN 201610295989A CN 105777583 A CN105777583 A CN 105777583A
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- 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
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Abstract
The invention provides a method for preparing methyl carbamate by a urea methanolysis method. The method comprises the following steps of adding methyl alcohol and urea into a high-pressure reaction kettle which is provided with a magnetic stirrer and a heating temperature control system, stirring for 20min at the temperature of 30 DEG C, and fully mixing; then, adding a catalyst Ni5Ca5(PO4)6F2, sending CO2 (carbon dioxide) into the reaction kettle for three times, replacing the air in the reaction kettle, and reacting for 2-10h at the CO2 pressure of 0.6MPa and the temperature of 120-170 DEG C in the reaction kettle, wherein the total mass ratio of the catalyst Ni5Ca5(PO4)6F2 and the reactants of urea and methyl alcohol is 1-5:100, and the molar ratio of methyl alcohol and urea is 15:1; lowering the temperature of the reaction system to the room temperature, filtering and removing the catalyst, and rotationally evaporating the methyl alcohol, so as to obtain a target product of methyl carbamate. The selectivity of the obtained methyl carbamate is 98.9%, the conversion rate of urea is 99.8%, and the maximum yield of methyl carbamate is 98.8%. The method for preparing the methyl carbamate has the characteristics that the preparation technology is simple, the reaction condition is mild, the yield of the target product is high, and the like; the method is a clean methyl carbamate preparation technology.
Description
Technical field
The invention belongs to fine chemistry industry green synthesis techniques field, relate to a kind of method that alcoholysis of urea prepares methyl carbamate.
Background technology
Methyl carbamate (Methyl Carbomate is called for short MC), chemical formula is NH2COOCH3, it is a kind of important fine chemicals, can be widely used as multiple additives, be also the important source material of medicine, pesticide, surfactant, modifier and Synthesis of dimethyl carbonate.
The method of synthesizing amino methyl formate mainly has phosgenation, organic carbonate amine-decomposing method, carbonylation method and alcoholysis of urea.Phosgenation, with phosgene as raw material, obtains methyl carbamate through alcoholysis and ammonolysis, and the method not only production cost is high, and serious environment pollution.Therefore, use non-phosgene to produce methyl carbamate and become the focus of people's research.Organic carbonate ester process is that this reaction conversion ratio and yield are relatively low, and by-product is more with organic carbonate and amine for Material synthesis methyl carbamate, and the response time longer (list of references, Industrial Catalysis, 2005,13(11): 30-33).Carbonylation method is primarily referred to as reacting with carbonyl source and organic amine for raw material, and it is more complicated that this reaction exists reaction mechanism, and in raw material, CO toxicity is big, explosive and utilization rate relatively low (list of references, modern chemical industry, 2009,66(29): 11-18).Alcoholysis of urea refers to carbamide and alcohols as reaction raw materials, the method for a step alcoholysis synthesizing amino methyl formate.The method reactions steps is simple, and raw material is abundance and with low cost, and economic benefit is the highest, is paid attention to the most widely, has good DEVELOPMENT PROSPECT.Zhang Zhaowen et al. discloses the preparation technology of a kind of methyl carbamate, it it is 100 ~ 180 DEG C in reaction temperature, reaction pressure 0.1 ~ 1.5 MPa, response time is under 0.5 ~ 10 h, through rectifying column, the ammonia methanol mixed vapor removal discharged in course of reaction being gone out ammonia and methanol, the productivity of methyl carbamate reaches as high as 91%.But it is relatively big (list of references, CN 1683326) that this reaction is constantly carried over reaction system, raw material dosage and energy consumption due to methanol.Deng You congruence people discloses the catalyst of a kind of alkyl carbamate synthesis, reaction temperature is 160 DEG C, course of reaction defines dimethyl carbonate, the by-products such as methylene dicarbamate, there is the low problem (list of references, CN 101518729A) separating difficulty with by-product of methyl carbamate yield.
Summary of the invention
For solving the problem that prior art exists, the present invention provides a kind of method that alcoholysis of urea prepares methyl carbamate.
The method that a kind of alcoholysis of urea that the present invention provides prepares methyl carbamate, step and condition are as follows:
(1) with magnetic stirring apparatus, heated for controlling temperature system autoclave in add methanol, carbamide, at 30 DEG C, stir 20 min and be allowed to be sufficiently mixed, be subsequently adding catalyst n i5Ca5(PO4)6F2, it is passed through CO2Three times, after the air in displacement still, CO in reactor2Pressure be 0.6 MPa, at temperature is 120 ~ 170 DEG C react 2-10 h, catalyst n i5Ca5(PO4)6F2Quality and reactant carbamide and the mol ratio that total mass ratio is 1-5:100, methanol and carbamide of methanol be 15:1；
( 2 )Reaction system drops to room temperature, Filtration of catalyst, and rotary evaporation goes out methanol, obtains object methyl carbamate.
The object methyl carbamate obtained, with the content of chromatographic wherein methyl carbamate.Chromatographiccondition is: gas chromatograph Agilent GC6890, analysis condition: HP-5 capillary column, fid detector, and injector temperature is 240 DEG C, and detector temperature is 280 DEG C.Sample size 1.0 μ L.
Beneficial effect:A kind of alcoholysis of urea method of preparing methyl carbamate that the present invention provides, with carbamide and methanol as raw material, with Ni5Ca5(PO4)6F2For catalyst, reaction medium is methanol, and the selectivity obtaining methyl carbamate is 98.9%, and conversion rate of urea is 99.8%,
The maximum yield of methyl carbamate is 98.8%.It is simple that the methyl carbamate production method of the present invention has preparation technology, and reaction condition is gentle, target product yield high, is the methyl carbamate preparation technology of cleaning.
Detailed description of the invention
Embodiment 1 :A kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition are as follows: (1) with magnetic stirring apparatus, heated for controlling temperature system autoclave in, add methanol, carbamide, at 30 DEG C, stir 20 min to be allowed to be sufficiently mixed, be subsequently adding catalyst n i5Ca5(PO4)6F2, it is passed through CO2Three times, after the air in displacement still, CO in reactor2Pressure be 0.6 MPa, at temperature is 160 DEG C, react 6 h, catalyst n i5Ca5(PO4)6F2Quality and reactant carbamide and the mol ratio that total mass ratio is 4:100, methanol and carbamide of methanol be 15:1；Concrete addition is: carbamide 1.0 g, methanol 10 mL, catalyst n i5Ca5(PO4)6F20.72
g；
( 2 )Reaction system drops to room temperature, Filtration of catalyst, and rotary evaporation goes out methanol, obtains target product methyl carbamate.
The object methyl carbamate obtained, with the content of chromatographic wherein methyl carbamate.Chromatographiccondition is: gas chromatograph Agilent GC6890, analysis condition: HP-5 capillary column, fid detector, and injector temperature is 240 DEG C, and detector temperature is 280 DEG C.Sample size 1.0 μ L.Testing result is shown in Table 1.
Embodiment 2 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 2 h at temperature is 160 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 3 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 4 h at temperature is 160 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 4 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 8 h at temperature is 160 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 5 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 10 h at temperature is 160 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 6 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: it is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 6 h at temperature is 120 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 7 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 6 h at temperature is 130 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 8 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 6 h at temperature is 140 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 9 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 6 h at temperature is 150 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 10 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), reacts 6 h at temperature is 170 DEG C；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 11 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), catalyst n i5Ca5(PO4)6F2Quality and reactant carbamide and the mass ratio of methanol be 1:100, be subsequently adding catalyst n i5Ca5(PO4)6F2, at temperature is 160 DEG C, react 6 h；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 12 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), catalyst n i5Ca5(PO4)6F2Quality and reactant carbamide and the mass ratio of methanol be 2:100, be subsequently adding catalyst n i5Ca5(PO4)6F2, at temperature is 160 DEG C, react 6 h；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 13 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), catalyst n i5Ca5(PO4)6F2Quality and reactant carbamide and the mass ratio of methanol be 3:100, be subsequently adding catalyst n i5Ca5(PO4)6F2, at temperature is 160 DEG C, react 6 h；Remaining is all with embodiment 1.Testing result is shown in Table 1.
Embodiment 14 :It is as follows that a kind of alcoholysis of urea prepares the method for methyl carbamate, step and condition: described step (1), catalyst n i5Ca5(PO4)6F2Quality and reactant carbamide and the mass ratio of methanol be 5:100, be subsequently adding catalyst n i5Ca5(PO4)6F2, at temperature is 160 DEG C, react 6 h；Remaining is all with embodiment 1.Testing result is shown in Table 1.
The data of table 1 show, alcoholysis of urea prepares the method for methyl carbamate, and the conversion rate of urea of embodiment 1 is 99.8%, and the selectivity of methyl carbamate is 98.9%, and the maximum yield of methyl carbamate is 98.8%.
Claims (2)
1. the method that an alcoholysis of urea prepares methyl carbamate, it is characterized in that, step and condition are as follows: (1) with magnetic stirring apparatus, heated for controlling temperature system autoclave in add methanol, carbamide, at 30 DEG C, stir 20 min to be allowed to be sufficiently mixed, be subsequently adding catalyst n i5Ca5(PO4)6F2, it is passed through CO2Three times, after the air in displacement still, CO in reactor2Pressure be 0.6 MPa, at temperature is 120 ~ 170 DEG C react 2-10 h, catalyst n i5Ca5(PO4)6F2Quality and reactant carbamide and the mol ratio that total mass ratio is 1-5:100, methanol and carbamide of methanol be 15:1；
(2)Reaction system drops to room temperature, Filtration of catalyst, and rotary evaporation goes out methanol, obtains object methyl carbamate.
The method that a kind of alcoholysis of urea the most as claimed in claim 1 prepares methyl carbamate, it is characterised in that described step (1), reacts 6 h, catalyst n i at temperature is 160 DEG C5Ca5(PO4)6F2Quality and reactant carbamide and the mol ratio that total mass ratio is 4:100, methanol and carbamide of methanol be 15:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631901A (en) * | 2016-12-14 | 2017-05-10 | 中榆化工科技有限公司 | Method for preparing methyl carbamate by urea alcoholysis method and device thereof |
| CN110590605A (en) * | 2019-10-11 | 2019-12-20 | 重庆化工职业学院 | Production method of methyl carbamate |
| CN114805132A (en) * | 2022-04-11 | 2022-07-29 | 长春工业大学 | Method for preparing methyl carbamate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631901A (en) * | 2016-12-14 | 2017-05-10 | 中榆化工科技有限公司 | Method for preparing methyl carbamate by urea alcoholysis method and device thereof |
| CN106631901B (en) * | 2016-12-14 | 2019-02-05 | 中榆化工科技有限公司 | A kind of method and device thereof preparing methyl carbamate using alcoholysis of urea |
| CN110590605A (en) * | 2019-10-11 | 2019-12-20 | 重庆化工职业学院 | Production method of methyl carbamate |
| CN110590605B (en) * | 2019-10-11 | 2021-08-24 | 重庆化工职业学院 | Production method of methyl carbamate |
| CN114805132A (en) * | 2022-04-11 | 2022-07-29 | 长春工业大学 | Method for preparing methyl carbamate |
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Application publication date: 20160720 |