CN110526837A - The method for preparing methyl carbamate as raw material using urea - Google Patents
The method for preparing methyl carbamate as raw material using urea Download PDFInfo
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- CN110526837A CN110526837A CN201910885416.9A CN201910885416A CN110526837A CN 110526837 A CN110526837 A CN 110526837A CN 201910885416 A CN201910885416 A CN 201910885416A CN 110526837 A CN110526837 A CN 110526837A
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- catalyst
- methyl carbamate
- urea
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- bismuth oxide
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention belongs to contain the compound technical of the amino and carboxyl that are connected on same carbon skeleton from natural products preparation, and in particular to a method of methyl carbamate is prepared by raw material of urea.The preparation method of the methyl carbamate, comprising the following steps: urea, methanol and catalyst are sequentially introduced into reactor, it is closed, react 4-6h at 130-150 DEG C to obtain the final product；The catalyst includes silica supported titanium dioxide-bismuth oxide.Methyl carbamate is prepared using method of the invention, the impurity contents such as class methyl carbamate are low, the high income of methyl carbamate.
Description
Technical field
The invention belongs to the compounding techniques necks from natural products preparation containing the amino and carboxyl being connected on same carbon skeleton
Domain, and in particular to a method of methyl carbamate is prepared by raw material of urea.
Background technique
Carbamate compound (Carbamic ester) tool has been widely used, and can be used as pesticide, medicine and has
The intermediate etc. of machine synthesis.Wherein, methyl carbamate (Methyl carbamate) is typical carbamates
Close object, structural formula NH2COOCH3, abbreviation MC, molecular weight 75.07, alias urethylan (Urethylane), methylurea
(Methylurethane), white crystals particle, soluble easily in water and alcohol, 177 DEG C of boiling point, relative density 1.1361, index of refraction
1.4125, pure 52-56.5 DEG C of quality requirement fusing point of chemistry.Methyl carbamate has a good application prospect, with it is tasteless,
Volatility is moderate, toxicity is low, mothproof effect is good, is to replace camphor better than mothproofing agents such as refined naphthalene, paracide, metaformaldehydes
One of ideal kind.In addition, methyl carbamate is applied very early as sedative, other insecticides,
Also there are preferable application, wide in variety, good drug efficacy in acaricide and fungicide.Methyl carbamate also acts as antiphlogistic, muscle
Relaxant, analgestic, antiepileptic.Methyl carbamate can be used for synthesizing the heterocyclic compounds such as N- substituent methyl pyrroles, imines ester
Object and alkene carry out addition reaction.Methyl carbamate can be used as cement additive, produce low-shrinkage cement, this cement
Shrinking percentage is low after solidification, and not crack.In textile industry, methyl carbamate replaces urea and formaldehyde condensation, then through two
The processes such as ethyl alcohol etherificate obtain the textile finshing agent for fiber treatment, and product is escaped with lower formaldehyde, wrinkle resistance in fabrics
It can be good.In coatings industry, powdery paints can be produced by raw material of methyl carbamate, the painting for household electrical appliances, instrument, meter case
Decorations, can increase the transparency and acid resistance of coating, have many advantages, such as that storage-stable is good, reactivity is high.In addition, amino first
Sour methyl esters also have in terms of surfactant and resin modified application (" urea method synthesizing amino methyl formate and its application into
Exhibition ", Zhu Mingqiao etc., Zhejiang chemical industry, the 8th phase of volume 34 in 2003, the left column paragraph 1 1-9 row of page 10, the left column the 4th of page 11
Section 1-6 row, the 5th section of 1-3 row of the left column of page 11, the 2nd section of the right column paragraph 1 1-5 row of page 11, the right column of page 11 1-2
Row, the 4th section of 1-2 row of the right column of page 11, the 6th section of the 5th section of 1-4 row of the right column of page 11, the right column of page 11 1-5 row, it is open
On December 18th, 2003 day；" technical study of alcoholysis of urea synthesizing amino methyl formate ", Li Liang, East China University of Science master
Academic dissertation, 2014,1-3 row of making a summary, publication date on December 31st, 2014).
However, the purity requirement of methyl carbamate is very high, product purity on the market is at least more than 98.5%, especially
It is medicine intermediate, purity requirement reaches 99.8%.If disregarding cost, using the purification technique means of modernization, essence is such as extracted
It evaporates, can achieve purity requirement, but cost will greatly improve, and be unfavorable for industry development, also can to the development of related industry
Cause biggish damage.
Inventor team and Bayer A.G once cooperated, and were catalysis with silica supported transition metal oxide
Agent has carried out relevant research to urea alcoholysis production methyl carbamate, in 150-170 DEG C of reaction temperature, the item of 8-12h
Synthesizing amino methyl formate under part, yield is up to 95%.However, inventor has found during the experiment, along with methyl carbamate
Generation, have the generation of about 0.5% class methyl carbamate, property and methyl carbamate are closely similar, separation very
It is difficult.However, to reach the medicine intermediate of 99.8% purity, it is necessary to reduce the generation of class methyl carbamate, improve amino first
The yield of sour methyl esters.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation methods of the methyl carbamate of high income.
To achieve the above object, the technical solution of the present invention is as follows:
The preparation method of methyl carbamate, comprising the following steps:
Urea, methanol and catalyst are sequentially introduced into reactor, it is closed, react 4-6h at 130-150 DEG C to obtain the final product；
The catalyst includes silica supported titanium dioxide-bismuth oxide.
Inventor has been surprisingly found that in the course of the research, comprising the following steps: is sequentially introduced into urea, methanol and catalyst
It is closed in reactor, react 4-6h at 130-150 DEG C to obtain the final product；
The catalyst includes silica supported titanium dioxide-bismuth oxide；
Method prepare methyl carbamate, the high income of methyl carbamate.
Further, the molar ratio of silica and bismuth oxide is 855.8:1-855.8:4 in the catalyst.
Further, the ratio between mole of bismuth oxide and titanium dioxide is 340:3950-340:1975 in the catalyst.
Further, the dosage of the catalyst is the 3%-7% of urea quality.
Further, the dosage of the methanol is the final concentration of 5-8g/100mL for making urea.
Further, the methyl carbamate preparation method the following steps are included:
Urea, methanol and catalyst are sequentially introduced into reactor, it is closed, react 4-6h at 130-150 DEG C to obtain the final product；It is described
The dosage of catalyst is the 3%-7% of urea quality, and the dosage of the methanol is the final concentration of 5-8g/100mL for making urea；
The catalyst includes silica supported titanium dioxide-bismuth oxide；Silica and bismuth oxide in the catalyst
Molar ratio be 855.8:1-855.8:4, the ratio between mole of bismuth oxide and titanium dioxide is 340:3950- in the catalyst
340:1975。
The second object of the present invention is to protect the catalyst for being used for catalyzing urea synthesizing amino methyl formate, the catalysis
Agent includes silica supported titanium dioxide-bismuth oxide.
Further, the molar ratio of silica and bismuth oxide is 855.8:1-855.8:4 in the catalyst.
Further, the ratio between mole of bismuth oxide and titanium dioxide is 340:3950-340:1975 in the catalyst.
Further, the catalyst, including silica supported titanium dioxide-bismuth oxide, dioxy in the catalyst
SiClx and the molar ratio of bismuth oxide are 855.8:1-855.8:4, the ratio between mole of bismuth oxide and titanium dioxide in the catalyst
For 340:3950-340:1975.
The present invention also aims to protect the preparation method of the catalyst, specifically includes the following steps:
Bismuth nitrate and butyl titanate are dissolved in nitric acid solution, after solution clarification, silica is added to above-mentioned solution
In, 3-6h is stood at room temperature, then in 80-120 DEG C of drying 3-6h, then at 450-600 DEG C roasts 3-6h.
Further, the mass ratio of bismuth nitrate and butyl titanate is 1:5-1:10.
Further, the concentration of nitric acid solution is 0.5-2mol/L.
Further, the molar ratio of silica and bismuth nitrate is 855.8:1-855.8:4.
The beneficial effects of the present invention are:
Methyl carbamate is prepared using method of the invention, the impurity contents such as class methyl carbamate are low.
Methyl carbamate, the high income of methyl carbamate, up to 98% or more are prepared using method of the invention.
Methyl carbamate is prepared using method of the invention, reaction condition is mild.
Catalyst of the invention is low in cost.
Specific embodiment
Illustrated embodiment is to preferably be illustrated to the contents of the present invention, but is not that the contents of the present invention only limit
In illustrated embodiment.So those skilled in the art carry out nonessential change to embodiment according to foregoing invention content
Into and adjustment, still fall within protection scope of the present invention.
With the detection method of lower class methyl carbamate content are as follows: be determined using gas chromatographic detection, the inspection of use
Survey device be hydrogen flame detector, chromatographic condition be 200 DEG C of injection port, 200 DEG C of detector, sample volume 0.5ul, chromatographic column HP-5
Column, column temperature initial temperature is 80 DEG C, with 10 DEG C/min temperature programming to 200 DEG C, keeps 10min；First with the class ammonia of various concentration
Base methyl formate makes external standard curve (external standard method), and the standard curve of production is straight line, and the concentration with class methyl carbamate is
Abscissa, the area of chromatographic peak are ordinate；The area of the class methyl carbamate periodically determined in reaction process corresponds to
The concentration of class methyl carbamate on standard curve, can calculate the content of methyl carbamate；
The detection method of methyl carbamate yield are as follows: be determined using gas chromatographic detection, the detector used is hydrogen fire
Flame detector, chromatographic condition are 200 DEG C of injection port, and 200 DEG C of detector, sample volume 0.5ul, chromatographic column HP-5 column, column temperature is initial
Temperature is 80 DEG C, with 10 DEG C/min temperature programming to 200 DEG C, keeps 10min；
Yield calculation formula are as follows: the amount of amount/urea substance of the substance of methyl carbamate；
The method of specific calculated yield are as follows: external standard curve (external standard method) is first made with the methyl carbamate of various concentration, system
The standard curve of work is straight line, and using the concentration of methyl carbamate as abscissa, the area of chromatographic peak is ordinate；Reaction process
The area for the methyl carbamate that middle timing determines corresponds to the concentration of methyl carbamate on standard curve, can calculate
The amount of methyl carbamate, and then calculate the yield of methyl carbamate.
Embodiment 1
The preparation of methyl carbamate, specific steps are as follows:
A. silica supported titanium dioxide-bismuth oxide catalyst is prepared
In the nitric acid solution for the 0.5mol/L that 0.1g bismuth nitrate and 0.5g butyl titanate are dissolved in 15ml, after solution clarification,
13g silica is added in above-mentioned solution, stands 3h at room temperature, then in 80 DEG C of drying 6h, is finally roasted at 450 DEG C
Catalyst A can be obtained in 3h；
B. methyl carbamate is produced
By 50g urea, 1000ml methanol and 1.5g catalyst A are sequentially introduced into 2L reaction kettle, closed, are heated to 150 DEG C, instead
Answer 6h to get to methyl carbamate, through detecting, the yield of methyl carbamate is 98%, class amino in methyl carbamate
Methyl formate content is 0.1%.
Embodiment 2
The preparation of methyl carbamate, specific steps are as follows:
A. silica supported titanium dioxide-bismuth oxide catalyst is prepared
In the nitric acid solution for the 2mol/L that 0.4g bismuth nitrate and 4g butyl titanate are dissolved in 15ml, after solution clarification, by 13g
Silica is added in above-mentioned solution, stands 6h at room temperature, then in 120 DEG C of drying 3h, finally roasts 3h at 600 DEG C,
Catalyst B can be obtained；
B. methyl carbamate is produced
By 71g urea, 1000ml methanol and 3.5g catalyst B are sequentially introduced into 2L reaction kettle, closed, are heated to 150 DEG C, instead
Answer 4h to get to methyl carbamate, through detecting, the yield of methyl carbamate is 99%, is not detected in methyl carbamate
To class methyl carbamate.
Embodiment 3
The preparation of methyl carbamate, specific steps are as follows:
A. silica supported titanium dioxide-bismuth oxide catalyst is prepared
In the nitric acid solution for the 1mol/L that 0.2g bismuth nitrate and 2g butyl titanate are dissolved in 15ml, after solution clarification, by 13g
Silica is added in above-mentioned solution, stands 4h at room temperature, then in 100 DEG C of drying 5h, finally roasts 4h at 520 DEG C,
Catalyst C can be obtained；
B. methyl carbamate is produced
By 80g urea, 1000ml methanol and 5.6g catalyst C are sequentially introduced into 2L reaction kettle, closed, are heated to 130 DEG C, instead
Answer 6h to get to methyl carbamate, through detecting, the yield of methyl carbamate is 99%, is not detected in methyl carbamate
To class methyl carbamate.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (10)
1. the preparation method of methyl carbamate, which comprises the following steps:
Urea, methanol and catalyst are sequentially introduced into reactor, it is closed, react 4-6h at 130-150 DEG C to obtain the final product；
The catalyst includes silica supported titanium dioxide-bismuth oxide.
2. preparation method according to claim 1, which is characterized in that silica and bismuth oxide rubs in the catalyst
You are than being 855.8:1-855.8:4.
3. preparation method according to claim 1 or 2, which is characterized in that bismuth oxide and titanium dioxide in the catalyst
The ratio between mole be 340:3950-340:1975.
4. preparation method according to claim 1-3, which is characterized in that the dosage of the catalyst is urea matter
The 3%-7% of amount.
5. preparation method according to claim 1-4, which is characterized in that the dosage of the methanol is to make urea
Final concentration of 5-8g/100mL.
6. preparation method according to claim 1-5, which comprises the following steps:
Urea, methanol and catalyst are sequentially introduced into reactor, it is closed, react 4-6h at 130-150 DEG C to obtain the final product；It is described
The dosage of catalyst is the 3%-7% of urea quality, and the dosage of the methanol is the final concentration of 5-8g/100mL for making urea；
The catalyst includes silica supported titanium dioxide-bismuth oxide；Silica and bismuth oxide in the catalyst
Molar ratio be 855.8:1-855.8:4, the ratio between mole of bismuth oxide and titanium dioxide is 340:3950- in the catalyst
340:1975。
7. being used for the catalyst of catalyzing urea synthesizing amino methyl formate, which is characterized in that including silica supported dioxy
Change titanium-bismuth oxide.
8. catalyst according to claim 7, which is characterized in that mole of silica and bismuth oxide in the catalyst
Than for 855.8:1-855.8:4.
9. according to the preparation method of the catalyst of claim 7 or 8, which comprises the following steps:
Bismuth nitrate and butyl titanate are dissolved in nitric acid solution, after solution clarification, silica is added to above-mentioned solution
In, 3-6h is stood at room temperature, then in 80-120 DEG C of drying 3-6h, then at 450-600 DEG C roasts 3-6h.
10. preparation method according to claim 9, which is characterized in that the mass ratio of bismuth nitrate and butyl titanate is 1:
5-1:10。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662215A (en) * | 2020-07-27 | 2020-09-15 | 重庆化工职业学院 | Process for preparing carbamates |
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| CN1475481A (en) * | 2003-07-11 | 2004-02-18 | 中国科学院山西煤炭化学研究所 | Method of synthesizing methyl carbamate |
| CN101121659A (en) * | 2007-09-29 | 2008-02-13 | 中国科学院山西煤炭化学研究所 | Technique for producing organic carbonic acid ester by urea alcoholysis method and fixed bed reactor |
| WO2011013880A2 (en) * | 2009-07-31 | 2011-02-03 | Korea Research Institute Of Chemical Technology | Method for preparing dialkyl carbonate |
| CN102190601A (en) * | 2010-03-11 | 2011-09-21 | 中国科学院兰州化学物理研究所 | Method for synthesizing micromolecular alkyl carbamate |
| CN103172538A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院兰州化学物理研究所 | Method for synthesis of carbamate under mild conditions |
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2019
- 2019-09-19 CN CN201910885416.9A patent/CN110526837A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475481A (en) * | 2003-07-11 | 2004-02-18 | 中国科学院山西煤炭化学研究所 | Method of synthesizing methyl carbamate |
| CN101121659A (en) * | 2007-09-29 | 2008-02-13 | 中国科学院山西煤炭化学研究所 | Technique for producing organic carbonic acid ester by urea alcoholysis method and fixed bed reactor |
| WO2011013880A2 (en) * | 2009-07-31 | 2011-02-03 | Korea Research Institute Of Chemical Technology | Method for preparing dialkyl carbonate |
| CN102190601A (en) * | 2010-03-11 | 2011-09-21 | 中国科学院兰州化学物理研究所 | Method for synthesizing micromolecular alkyl carbamate |
| CN103172538A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院兰州化学物理研究所 | Method for synthesis of carbamate under mild conditions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662215A (en) * | 2020-07-27 | 2020-09-15 | 重庆化工职业学院 | Process for preparing carbamates |
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