CN1241908C - Method of synthesizing methyl carbamate - Google Patents
Method of synthesizing methyl carbamate Download PDFInfo
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- CN1241908C CN1241908C CN 03145678 CN03145678A CN1241908C CN 1241908 C CN1241908 C CN 1241908C CN 03145678 CN03145678 CN 03145678 CN 03145678 A CN03145678 A CN 03145678A CN 1241908 C CN1241908 C CN 1241908C
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- reaction
- urea
- catalyzer
- pressure
- formiate
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000035484 reaction time Effects 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- -1 Methyl Carbomate Chemical compound 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229960005286 carbaryl Drugs 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002557 soporific effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940125725 tranquilizer Drugs 0.000 description 1
- 239000003204 tranquilizing agent Substances 0.000 description 1
- 230000002936 tranquilizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for synthesizing methyl carbamate. Methanol, urea and a catalyst are added into a reactor according to the mol proportion of the methanol and the urea of 1 to 100: 1 and the mol proportion of the catalyst and the urea of 0.001 to 10: 1 to react under the conditions of temperature is from 120 to 200 DEG C, and reaction pressure is from 0.1 to 3.0MPa. When the pressure in the reactor is greater than reaction pressure, ammonia gas generated in the reaction is discharged and recovered after the ammonia gas is condensed. Reaction time is 0.5h to 20h. The present invention has the advantages of cheap and easy obtained raw materials, the high selectivity of reaction products, few side products, simple reaction process and easy operation.
Description
Affiliated field:
The invention belongs to a kind of method of synthesizing amino methyl-formiate.
Background technology:
Urethylane (Methyl Carbomate is called for short MC), claim urethane again, it is a kind of intermediate of organic synthesis, be mainly used in and make weedicide, agricultural chemicals and plastic working, can also be used for synthetic soporific, tranquilizer, and the tinting material of toxinicide, injection, solubility promoter and the printing and dyeing industry of vauqueline, Resorcino, also can be used as biochemical reagents, be used for biochemical research.Simultaneously, Urethylane is again the reaction raw materials of Synthesis of dimethyl carbonate.
Early stage Urethylane is mainly made by amine photoreactive gas or chloro-formic ester reaction, not only serious environment pollution and production cost costliness.In recent years, abroad developed in succession by carbon monoxide, alcohols and nitro-compound reaction and produced the Urethylane novel process, produce the Urethylane operational path from methylcarbonate and amine reaction, used catalyst system is mainly organic zinc, organotin or organic cobalt and sodium methylate, sodium ethylate, pyridine and indoles etc.On the one hand, these catalyst reaction temperatures＞200 ℃, pressure 20～60atm, severe reaction conditions, the carbamate yield is low, poor selectivity; On the other hand, used reaction raw materials costliness, production cost exists the potential economy, and anti-market interference performance is poor.
Summary of the invention:
The purpose of this invention is to provide a kind of is raw material with urea and methyl alcohol, high yield, the method for synthesizing amino methyl-formiate cheaply.
The object of the present invention is achieved like this: with urea and methyl alcohol is raw material, in the presence of solid base catalyst, react the synthesizing amino methyl-formiate, and adopt novel reactor to be beneficial to react in time the ammonia that generates and shift out reaction system, thereby improve the yield of Urethylane.Synthetic method of the present invention comprises the steps:
Is 1-100 with methyl alcohol, urea and catalyzer by the molar ratio of methyl alcohol and urea: 1, the molar ratio of catalyzer and urea is 0.001-10: 1 adds in the reactor, at temperature 120-200 ℃, reaction pressure is to react under the condition of 0.1-3.0Mpa, pressure in the reactor is during greater than reaction pressure, the ammonia that reaction generates is discharged after condensation, is reclaimed, and the reaction times is 0.5h-20h.
Aforesaid catalyzer is the oxide compound of basic metal, alkaline-earth metal, comprises the oxide compound of Ca, Zn, K, Mg, Na, Pb etc.Decompose by coprecipitation method or corresponding metal salt or alkali and to form.
Catalyzer also may be the soild oxide that impregnated in one or more the above-mentioned metals on the carrier.Wherein carrier comprises various gacs, aluminum oxide, silicon oxide, molecular sieve etc.
The present invention compared with prior art has following advantage:
1) reaction raw materials is cheap and easy to get, and the selectivity of reaction product is higher, and by product is less, so the economy highly significant of building-up process;
2) reaction process is simple, easy handling, and catalyst performance repeatability is relatively good, realizes the industry amplification easily.
Embodiment:
Embodiment 1:
The ca nitrate soln of configuration 15%.Down carry out co-precipitation with the sodium carbonate solution of 30 (Wt) % at 70 ℃, precipitation process needs fully to stir, and keeps pH=9, precipitation through distilled water wash to neutral, 120 ℃ of dryings and through 350 ℃ of roastings down.Be reflected in the autoclave of 70ml and carry out, with the heating of electrically heated cover, catalyst levels is 1.5g, urea 6.05g, methyl alcohol 16g, 170 ℃ of temperature of reaction, reaction pressure 2.0MPa, pressure in the reactor is greater than 2.0MPa, and the ammonia that reaction generates is discharged after condensation, reclaimed, reaction times 1.5h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 95.90 | 98.81 |
Embodiment 2. catalyzer are CaO, and (catalyzer is by CaCO
3Roasting makes)
Catalyst levels is 1.5g, urea 15g, and methyl alcohol 32g, 150 ℃ of temperature of reaction, reaction pressure 1.8MPa, the pressure in the reactor are greater than 1.8MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 3h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 96.30 | 97.78 |
Embodiment 3. catalyzer are commercial ZnO
Catalyst levels is 2.5g, urea 6g, and methyl alcohol 160g, 180 ℃ of temperature of reaction, reaction pressure 3.0MPa, the pressure in the reactor are greater than 3.0MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 2h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 98.33 | 98.73 |
Embodiment 4. catalyzer are ZnO, and (catalyzer is by Zn (OH)
2Roasting makes)
Catalyst levels is 1g, urea 6g, and methyl alcohol 8g, 200 ℃ of temperature of reaction, reaction pressure 1.0MPa, the pressure in the reactor are greater than 1.0MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 1h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 96.21 | 97.05 |
Embodiment 5. catalyzer are MgO, and (catalyzer is by Mg (OH)
2Roasting makes)
Catalyst levels is 1.5g, urea 6g, and methyl alcohol 24g, 170 ℃ of temperature of reaction, reaction pressure 4.0MPa, the pressure in the reactor are greater than 4.0MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 3h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 97.28 | 98.09 |
Embodiment 6. catalyzer are ZnO, (catalyzer is made by commercial ZnO roasting)
Catalyst levels is 2g, urea 6g, and methyl alcohol 16g, 170 ℃ of temperature of reaction, reaction pressure 5.0MPa, the pressure in the reactor are greater than 5.0MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 1.5h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 96.88 | 97.23 |
Embodiment 7. catalyzer are PbO, and (catalyzer is by Pb (Ac)
2Roasting makes)
Catalyst levels is 1.5g, urea 6g, and methyl alcohol 32g, 175 ℃ of temperature of reaction, reaction pressure 2.0MPa, the pressure in the reactor are greater than 2.0MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 3h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 95.26 | 97.55 |
Embodiment 8. catalyzer are ZnO/SiO
2, (catalyzer is made by pickling process, and the content of ZnO is 20Wt%)
Catalyst levels is 10g, urea 6g, and methyl alcohol 30g, 150 ℃ of temperature of reaction, reaction pressure 2.0MPa, the pressure in the reactor are greater than 2.0MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 2h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 95.63 | 98.28 |
Embodiment 9. catalyzer are MgO/C, (catalyzer is made by pickling process, and the content of MgO is 10Wt%)
Catalyst levels is 20g, urea 6g, and methyl alcohol 16g, 160 ℃ of temperature of reaction, reaction pressure 2.5MPa, the pressure in the reactor are greater than 2.5MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 2.5h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 95.68 | 97.39 |
Embodiment 10. does not add catalyzer, urea 6g, and methyl alcohol 12g, 165 ℃ of temperature of reaction, reaction pressure 2.0MPa, the pressure in the reactor are greater than 2.0MPa, and the ammonia that reaction generates is discharged after condensation, is reclaimed, reaction times 7h.The gained result is as follows:
| Conversion rate of urea % | MC yield % |
| 50.72 | 45.90 |
Claims (5)
1. the method for a synthesizing amino methyl-formiate, it is characterized in that be 1-100 with methyl alcohol, urea and catalyzer by the molar ratio of methyl alcohol and urea: 1, the molar ratio of catalyzer and urea is 0.001-10: 1 adds in the reactor, at temperature 120-200 ℃, reaction pressure is to react under the condition of 0.1-3.0Mpa, pressure in the reactor is during greater than reaction pressure, and the ammonia that reaction generates is discharged after condensation, reclaimed, and the reaction times is 0.5h-20h;
Wherein catalyzer is the oxide compound of basic metal, alkaline-earth metal, Zn, Pb.
2. the method for a kind of synthesizing amino methyl-formiate as claimed in claim 1, the oxide compound that it is characterized in that described basic metal, alkaline-earth metal are to be decomposed by coprecipitation method or corresponding metal salt or alkali to form.
3. the method for a kind of synthesizing amino methyl-formiate as claimed in claim 2, the oxide compound that it is characterized in that described basic metal, alkaline-earth metal be Ca,, the oxide compound of K, Mg or Na.
4. the method for a kind of synthesizing amino methyl-formiate as claimed in claim 1 is characterized in that catalyzer is the soild oxide that impregnated in one or more metals on the carrier.
5. the method for a kind of synthesizing amino methyl-formiate as claimed in claim 4 is characterized in that carrier comprises gac, aluminum oxide, silicon oxide, molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03145678 CN1241908C (en) | 2003-07-11 | 2003-07-11 | Method of synthesizing methyl carbamate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03145678 CN1241908C (en) | 2003-07-11 | 2003-07-11 | Method of synthesizing methyl carbamate |
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| Publication Number | Publication Date |
|---|---|
| CN1475481A CN1475481A (en) | 2004-02-18 |
| CN1241908C true CN1241908C (en) | 2006-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03145678 Expired - Fee Related CN1241908C (en) | 2003-07-11 | 2003-07-11 | Method of synthesizing methyl carbamate |
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| Country | Link |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357266C (en) * | 2005-02-21 | 2007-12-26 | 东营市康瑞石油化工有限责任公司 | Process for producing methyl carbamate |
| CN100415712C (en) * | 2005-02-21 | 2008-09-03 | 东营市康瑞石油化工有限责任公司 | Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction |
| CN101518729B (en) * | 2008-02-26 | 2013-04-24 | 拜耳材料科技(中国)有限公司 | Catalyst used for synthesizing alkyl carbamate and preparing method and application thereof |
| CN101570499A (en) * | 2009-03-07 | 2009-11-04 | 垦利三合新材料科技有限责任公司 | Preparation method of methyl carbamate |
| CN101863800B (en) | 2009-04-14 | 2015-06-24 | 拜耳材料科技(中国)有限公司 | Method for synthesizing carbamate, catalyst applicable to method and preparation method and use thereof |
| 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 |
| CN103524381A (en) * | 2013-10-14 | 2014-01-22 | 中国科学院山西煤炭化学研究所 | Synthesis of N-methylmethyl carbamate |
| CN105753740B (en) * | 2016-04-06 | 2017-08-04 | 哈尔滨师范大学 | A kind of process for catalytic synthesis of methyl carbamate |
| CN105777583A (en) * | 2016-05-07 | 2016-07-20 | 长春工业大学 | Method for preparing methyl carbamate by urea methanolysis method |
| CN106669654A (en) * | 2016-12-14 | 2017-05-17 | 中榆化工科技有限公司 | Catalyst for preparing methyl carbamate and preparation method of catalyst |
| 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 |
| CN110526837A (en) * | 2019-09-19 | 2019-12-03 | 重庆化工职业学院 | The method for preparing methyl carbamate as raw material using urea |
| CN111662215A (en) * | 2020-07-27 | 2020-09-15 | 重庆化工职业学院 | Process for preparing carbamates |
-
2003
- 2003-07-11 CN CN 03145678 patent/CN1241908C/en not_active Expired - Fee Related
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