CN102190601A - Method for synthesizing micromolecular alkyl carbamate - Google Patents
Method for synthesizing micromolecular alkyl carbamate Download PDFInfo
- Publication number
- CN102190601A CN102190601A CN200910221167XA CN200910221167A CN102190601A CN 102190601 A CN102190601 A CN 102190601A CN 200910221167X A CN200910221167X A CN 200910221167XA CN 200910221167 A CN200910221167 A CN 200910221167A CN 102190601 A CN102190601 A CN 102190601A
- Authority
- CN
- China
- Prior art keywords
- reaction
- urea
- carbamate
- separation system
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing micromolecular alkyl carbamate. In the method, a reaction separation system consisting of a tank reactor and a gas storage-condensation-ammonium carbamate/ammonium carbonate catcher is used, carbon dioxide is used as an absorbent for a reaction byproduct of ammonia, accelerator for the reaction and another carbonyl source, and under the conditions that a mass ratio of alcohol to urea is 3/1-8/1, a mass ratio of a catalyst to urea is 0.01/1-0.2/1, the reaction temperature is 150-180DEG C, the pressure of the carbon dioxide is 0.7 to 2.3MPa, and the reaction time is 4 to 8 hours, the yield of the alkyl carbamate, which is obviously higher than that prepared from urea directly, is achieved (the yield is 100-108 percent, while the yield of the alkyl carbamate prepared from urea directly is 90 to 96 percent.). Moreover, the byproducts, namely the ammonia and a small amount of water generated in the reaction process are reacted with the carbon dioxide to generate ammonium carbamate or ammonium carbonate solid, so that the effect of timely removing the byproduct of ammonia, and the volume of a gas storage tank of the reactor is greatly reduced or the blowing of nitrogen (or gaseous methanol or ethanol) is avoided; therefore, the reaction operation is simplified and the production cost is reduced.
Description
Technical field
The present invention relates to a kind of method of synthesized micromolecule alkyl carbamate.
Background technology
Amino formate compounds (English carbamate or urethane) has purposes widely, can be used as the intermediate of agricultural chemicals, medicine and organic synthesis, as synthetic polyurethane, weedicide, agrochemical (P.Adames, F.Baron, Chem.Rev.65,1965).Urethylane (methyl carbamate) can be used for synthesizing isocyanate, melamine derivative and polyvinylamine etc. as the intermediate of organic synthesis; Can with reactions such as unsaturated hydrocarbons, aldehyde ketone, polyvalent alcohol and aromatic ring, generate the derivative of various uses; Because it has tasteless, characteristics such as volatility is moderate, toxicity is low, mothproof effect 100%, can replace naphthalene and camphor etc. as the agent of clothing favorable moth-proof; Urethanum (ethylcarbamate) not only itself can be used as medicine, and is the critical reactants of synthetic a kind of up-and-coming tranquilizer alkyl diol formic acid dialkyl, (USP:2837561); Butyl carbamate (butyl carbamate) and formaldehyde reaction generate the derivative of methylol, as the wrinkle resistant reagent of textile materials, (USP:3574711); These carbamates also can be used as the reaction raw materials of synthetic corresponding dialkyl carbonate simultaneously.
The carbonic acid gas conduct is the abundantest, recyclable, environmental friendliness and cheap C1 resource, and being translated into useful compound has important environment and economic implications.But because the inertia of carbonic acid gas, this is directly utilized carbonic acid gas to cause very big difficulty.Aspect alkyl carbamate synthetic, a kind of method of indirect utilization carbonic acid gas synthesizing amino alkyl formate has caused concern, just utilizes catalyzing urea alcoholysis method synthesizing amino alkyl formate.In the patent before us, the Deng You congruence utilizes silica supported transition metal oxide compound to be catalyzer synthesized micromolecule alkyl carbamate under the alcoholuria mol ratio of 8/1-20/1, can obtain yield (the Deng You congruence of the alkyl carbamate more than 90%, be used for alkyl carbamate synthetic Catalysts and its preparation method and purposes, CN101518729).Though this patent has solved problems such as the separation of catalyzer and repeated use, the alcoholuria mol ratio is still higher, causes reactor volume bigger, and production efficiency is not satisfactory.A prior problem is, for obtaining high yield, the by product ammonia must in time shift out reaction zone by continuous feeding nitrogen in the reaction process, and this difficulty that has also increased operation has improved production cost.Therefore, from industrial point of practical use, be necessary to develop a kind of at lower alcoholuria ratio, operating process and the reactor assembly of simplifying, high yield is the method for catalytically synthesizing small molecular alkyl carbamate efficiently.
Summary of the invention
The method that the purpose of this invention is to provide a kind of synthesized micromolecule alkyl carbamate.
We discover, in the presence of specific catalyst, the alcoholysis of urea methyl alcohol generates in the Urethylane process, partly compares for nitrogen atmosphere with the gas phase in the reactor, and conversion rate of urea obviously improves under carbon dioxide atmosphere.This may be to show combining of the ammonia that forms in tart carbonic acid gas and the reaction process, thereby has improved the yield of conversion rate of urea and target product, and carbonic acid gas plays the effect of absorption by product ammonia and promotor to reaction.Generate in the process of corresponding alkyl carbamate at urea ethanol or butanols catalyzed alcoholysis, carbonic acid gas except have above-mentioned to reaction play absorb and the effect of promotor, the by product ammonia that forms in the reaction generates extra corresponding alkyl carbamate having can further react in the presence of carbonic acid gas and ethanol or the butanols, thereby makes the yield of corresponding alkyl carbamate apparently higher than the yield of the alkyl carbamate that directly obtains from urea.Ammonia that produces in the reaction and carbon dioxide reaction generate ammonium carbamate or volatile salt solid, not only play the effect of effectively removing ammonia from reaction zone, also can reduce the volume of the incidental gas-holder of reactor greatly or avoid the purging of nitrogen (or gaseous state first or ethanol), avoid comparatively complicated pressure condition constantly to replenish the tripping device of first or alcoholic acid device and first or ethanol and ammonia down.And, compare with adopting nitrogen purging, adopt promotor or the additional carbonyl source of carbonic acid gas as ammonia absorption agent and reaction, can also obviously reduce the alcoholuria ratio.Thereby improved reaction yield and efficient, simplified operation, reactor assembly and reduced production cost.Generate ammonium carbamate or volatile salt solid and the further reaction of water in the reaction and can generate the volatile salt chemical, thereby make entire reaction course realize " zero release " substantially.
The present invention utilizes the absorption agent of carbonic acid gas for the by product ammonia of reaction, the promotor and the additional carbonyl source of reaction, in tank reactor, realize urea respectively with methyl alcohol, ethanol and butanols reaction, lower alcoholuria than under synthetic corresponding Urethylane, urethanum and the butyl carbamate of efficient and high yield.
A kind of method of synthesized micromolecule alkyl carbamate, it is characterized in that using carbonic acid gas as the promotor of ammonia absorption agent and reaction and the additional carbonyl source of reaction, in the reaction and separation system of tank reactor and gas storage-condensation-ammonium carbamate/volatile salt grabber formation, adopt silica supported titanium chromium composite oxide catalysts, catalysis methanol, ethanol or propyl carbinol and urea reaction, acquisition is apparently higher than the yield that directly obtains corresponding alkyl carbamate from urea (100-108%, the yield of the alkyl carbamate that directly obtains from urea is 90-96%).
A kind of method of synthesized micromolecule alkyl carbamate is characterized in that reaction and the separation system of using tank reactor and gas storage-condensation-ammonium carbamate/volatile salt grabber to constitute.The aspect ratio of separation system is 40/1-60/1, and volume is the 15-30% of reactor body, and in the reaction process, the temperature of separation system is at the 0-50 degree; The aspect ratio of tank reactor is 1.5/1-3/1, and temperature of reaction is 150-180 ℃.Separation system links to each other with the top of tank reactor.
A kind of method of synthesized micromolecule alkyl carbamate, it is characterized in that in the reaction process, the carbonic acid gas of 0-1MPa is introduced in the Reaction Separation system of tank reactor and gas storage-condensation-ammonium carbamate/volatile salt grabber formation, when waiting to be raised to temperature of reaction, adopt the lasting supplying carbon dioxide of the pressure (0.7-2.3MPa) identical in reaction system with reaction system.
A kind of method of synthesized micromolecule alkyl carbamate, it is characterized in that adopting silica supported titanium chromium composite oxide catalysts, the quality loading of titanium is that the quality loading of 1.4-5%, chromium is 3.5-9%, and silicon-dioxide is the bead of size 4-8mm radius.
A kind of method of synthesized micromolecule alkyl carbamate is characterized in that employed alcohol is 3/1-8/1 to urea mol ratio, and employed catalyzer is 0.05/1-0.2/1 to the mass ratio of urea, and temperature of reaction is 150-180 ℃; Reaction times is 2-8 hour, and the reaction times is 3-6 hour preferably.
The present invention is under the promoter action of carbonic acid gas, the urea transformation rate can improve 15-20%, add the additional carbonyl source of carbonic acid gas as reaction, can obtain the yield of the small molecules alkyl carbamate of 100-108%, and the yield of the alkyl carbamate that directly obtains from urea only is 90-96%.
Compare with alcoholysis of urea synthesizing amino alkyl formate compounds in the past, the substantive distinguishing features that the present invention has is:
1. the yield of alkyl carbamate is apparently higher than the yield of the alkyl carbamate that directly obtains from urea.
2. lower alcoholuria ratio, shorter reaction times and littler reactor volume.
3. simplify operation, reduce production costs and environment friendly more.
Description of drawings
Fig. 1 is the Reaction Separation system that tank reactor and gas storage-condensation-ammonium carbamate/volatile salt grabber constitute.
Embodiment
Embodiment 1:
Get in the beaker that the 4.0ml tetra-n-butyl titanate joins 100ml respectively, add the aqueous nitric acid that 10ml concentration is 24-27wt% then, the chromium nitrate that adds 7.692g again is to containing in the 4ml tetra-n-butyl titanate 100ml beaker, add silica dioxide granule 10g again through 600 ℃ of high temperature pre-treatment 2h, at room temperature flooded 4 hours, drying is 4 hours under 90 ℃, and roasting is 4 hours in 500 ℃ of air, makes catalyst A.
Embodiment 2:
13g catalyst A, 1000ml propyl carbinol, 130g urea join in the Reaction Separation system that 2000ml tank reactor and 500ml gas storage-condensation-ammonium carbamate/volatile salt grabber constitutes successively, airtightly are heated to 170 ℃, reaction 6h.Recording the urea transformation rate after reaction finishes is 83%, and the separation yield of butyl carbamate is 81%.
Embodiment 3:
With the 13g catalyst A, 1000ml propyl carbinol, 130g urea join in the Reaction Separation system that 2000ml tank reactor and 500ml gas storage-condensation-ammonium carbamate/volatile salt grabber constitutes successively, airtightly are heated to 170 ℃, reaction 6h.When temperature of reaction is raised to 170 when spending, the pressure of reactor is 0.7MPa, and the supplying carbon dioxide that continue with the pressure carbon dioxide of 0.7MPa this moment finishes until reaction in reactor.Recording the urea transformation rate after reaction finishes is 100%, the separation yield of butyl carbamate is 108%, ammonia that produces in the reaction process and carbonic acid gas are present on the inwall of gas storage-condensation-carboxylamine amine/volatile salt grabber with the solid form, and quality is about 55g.
Embodiment 4:
With the 15g catalyzer, the 1000ml dehydrated alcohol, 150g urea joins in the Reaction Separation system of 2000ml tank reactor and 500ml gas storage-condensation-ammonium carbamate/volatile salt grabber formation successively, airtight, nitrogen with 0.75MPa is incorporated in the reactor then, be heated to 170 ℃, reaction 8h.Recording the urea transformation rate after reaction finishes is 78%, and the separation yield of urethanum is 75%.
Embodiment 5:
With the 15g catalyzer, the 1000ml dehydrated alcohol, 150g urea joins in the Reaction Separation system of 2000ml tank reactor and 500ml gas storage-condensation-ammonium carbamate/volatile salt grabber formation successively, airtight, carbonic acid gas with 0.6MPa is incorporated in the reactor then, be heated to 170 ℃, reaction 8h.When temperature of reaction is raised to 170 when spending, the pressure of reactor is 1.7MPa, and the supplying carbon dioxide that continue with the pressure carbon dioxide of 1.7MPa this moment finishes until reaction in reactor.Recording the urea transformation rate after reaction finishes is 95%, the separation yield of urethanum is 100%, ammonia that produces in the reaction process and carbonic acid gas are present on the inwall of gas storage-condensation-carboxylamine amine/volatile salt grabber with the solid form, and quality is about 70g.
Embodiment 6:
With the 18g catalyzer, the 1000ml anhydrous methanol, 180g urea joins in the Reaction Separation system of 2000ml tank reactor and 500ml gas storage-condensation-ammonium carbamate/volatile salt grabber formation successively, airtight, nitrogen with 1.22MPa is incorporated in the reactor then, be heated to 170 ℃, reaction 8h.Recording the urea transformation rate after reaction finishes is 67%, and the separation yield of Urethylane is 64%.
Embodiment 7:
With the 18g catalyzer, the 1000ml anhydrous methanol, 180g urea joins in the Reaction Separation system of 2000ml tank reactor and 500ml gas storage-condensation-ammonium carbamate/volatile salt grabber formation successively, airtight, carbonic acid gas with 0.6MPa is incorporated in the reactor then, be heated to 170 ℃, reaction 8h.When temperature of reaction is raised to 170 when spending, the pressure of reactor is 2.3MPa, and the supplying carbon dioxide that continue with the pressure carbon dioxide of 1.7MPa this moment finishes until reaction in reactor.Recording the urea transformation rate after reaction finishes is 98%, and the separation yield of Urethylane is 95%.
Claims (6)
1. the method for a synthesized micromolecule alkyl carbamate, it is characterized in that using carbonic acid gas as the promotor of ammonia absorption agent and reaction and the additional carbonyl source of reaction, in the reaction and separation system of tank reactor and gas storage-condensation-ammonium carbamate/volatile salt grabber formation, adopt silica supported titanium chromium composite oxide catalysts, catalysis methanol, ethanol or propyl carbinol and urea reaction, the directly alkyl carbamate of Huo Deing.
2. the method for claim 1 is characterized in that reaction and the separation system of using tank reactor and gas storage-condensation-ammonium carbamate/volatile salt grabber to constitute; The aspect ratio of separation system is 40/1-60/1, and volume is the 15-30% of reactor body, and in the reaction process, the temperature of separation system is at the 0-50 degree; The aspect ratio of tank reactor is 1.5/1-3/1, and temperature of reaction is 150-180 ℃; Separation system links to each other with the top of tank reactor.
3. the method for claim 1, it is characterized in that in the reaction process, the carbonic acid gas of 0-1MPa is introduced in the Reaction Separation system of tank reactor and gas storage-condensation-ammonium carbamate/volatile salt grabber formation, when waiting to be raised to temperature of reaction, adopting the pressure identical with reaction system is that the lasting supplying carbon dioxide of 0.7-2.3MPa is in reaction system.
4. the method for claim 1, it is characterized in that adopting silica supported titanium chromium composite oxide catalysts, the quality loading of titanium is that the quality loading of 1.4-5%, chromium is 3.5-9%, and silicon-dioxide is the bead of size 4-8mm radius.
5. the method for claim 1 is characterized in that employed alcohol is 3/1-8/1 to urea mol ratio, and employed catalyzer is 0.05/1-0.2/1 to the mass ratio of urea, and temperature of reaction is 150-180 ℃; Reaction times is 2-8 hour.
6. method as claimed in claim 5 is characterized in that the reaction times is 3-6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910221167XA CN102190601A (en) | 2010-03-11 | 2010-03-11 | Method for synthesizing micromolecular alkyl carbamate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910221167XA CN102190601A (en) | 2010-03-11 | 2010-03-11 | Method for synthesizing micromolecular alkyl carbamate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102190601A true CN102190601A (en) | 2011-09-21 |
Family
ID=44599563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910221167XA Pending CN102190601A (en) | 2010-03-11 | 2010-03-11 | Method for synthesizing micromolecular alkyl carbamate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102190601A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104355955A (en) * | 2014-10-20 | 2015-02-18 | 华南理工大学 | Method for synthetizing carbamate |
| 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 |
| CN110590605A (en) * | 2019-10-11 | 2019-12-20 | 重庆化工职业学院 | Production method of methyl carbamate |
| CN117326982A (en) * | 2022-09-30 | 2024-01-02 | 四川元理材料科技有限公司 | Industrial process for synthesizing isophorone dicarbamic acid n-butyl ester by urea method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223638A (en) * | 1991-04-29 | 1993-06-29 | Monsanto Company | Preparation of urethane and carbonate products |
| CN1533362A (en) * | 2001-07-24 | 2004-09-29 | Dsm Ip�Ʋ�����˾ | Method for obtaining ammonium carbamate solution from gas mixture containing NH3, H2O and CO2 |
| CN101518729A (en) * | 2008-02-26 | 2009-09-02 | 拜耳材料科技贸易(上海)有限公司 | Catalyst used for synthesizing alkyl carbamate and preparing method and application thereof |
-
2010
- 2010-03-11 CN CN200910221167XA patent/CN102190601A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223638A (en) * | 1991-04-29 | 1993-06-29 | Monsanto Company | Preparation of urethane and carbonate products |
| CN1533362A (en) * | 2001-07-24 | 2004-09-29 | Dsm Ip�Ʋ�����˾ | Method for obtaining ammonium carbamate solution from gas mixture containing NH3, H2O and CO2 |
| CN101518729A (en) * | 2008-02-26 | 2009-09-02 | 拜耳材料科技贸易(上海)有限公司 | Catalyst used for synthesizing alkyl carbamate and preparing method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| 于剑峰等: "甲醇尿素均相催化合成氨基甲酸甲酯的研究", 《石油与天然气化工》, vol. 34, no. 4, 31 December 2005 (2005-12-31), pages 234 - 238 * |
| 戴春华等: "尿素醇解法合成氨基甲酸正丙酯的研究", 《石油与天然气化工》, vol. 36, no. 6, 31 December 2007 (2007-12-31) * |
| 李伍林等: "尿素醇解法合成氨基甲酸酯类化合物", 《化学与生物工程》, vol. 23, no. 1, 31 December 2006 (2006-12-31), pages 58 - 59 * |
| 李萍等: "尿素和甲醇反应制氨基甲酸甲酯的研究", 《工业催化》, vol. 14, no. 12, 31 December 2006 (2006-12-31), pages 47 - 50 * |
| 王欣欣等: "尿素醇解法合成氨基甲酸乙酯", 《广东化工》, vol. 34, no. 7, 31 December 2007 (2007-12-31), pages 16 - 18 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104355955A (en) * | 2014-10-20 | 2015-02-18 | 华南理工大学 | Method for synthetizing carbamate |
| 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 |
| 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 |
| CN117326982A (en) * | 2022-09-30 | 2024-01-02 | 四川元理材料科技有限公司 | Industrial process for synthesizing isophorone dicarbamic acid n-butyl ester by urea method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | A short review of catalysis for CO2 conversion | |
| Cheng et al. | Fabrication of robust and bifunctional cyclotriphosphazene-based periodic mesoporous organosilicas for efficient CO2 adsorption and catalytic conversion | |
| Leino et al. | Conventional synthesis methods of short-chain dialkylcarbonates and novel production technology via direct route from alcohol and waste CO2 | |
| CN101518729B (en) | Catalyst used for synthesizing alkyl carbamate and preparing method and application thereof | |
| Shang et al. | CO 2 activation and fixation: highly efficient syntheses of hydroxy carbamates over Au/Fe 2 O 3 | |
| Dibenedetto et al. | Synthesis of organic carbonates | |
| Wang et al. | N-Substituted carbamate synthesis using urea as carbonyl source over TiO 2–Cr 2 O 3/SiO 2 catalyst | |
| Wang et al. | Two-step synthesis of dimethyl carbonate from urea, ethylene glycol and methanol using acid–base bifunctional zinc-yttrium oxides | |
| CN102190601A (en) | Method for synthesizing micromolecular alkyl carbamate | |
| Zhang et al. | A strategy to overcome the thermodynamic limitation in CO 2 conversion using ionic liquids and urea | |
| Wang et al. | Transformation of CO 2 into polyureas with 3-amino-1, 2, 4-triazole potassium as a solid base catalyst | |
| Fang et al. | Direct oxidative carboxylation of olefins into cyclic carbonates at ambient pressure | |
| JP6305989B2 (en) | Method for producing dimethyl carbonate | |
| CN105618126A (en) | High-activity catalyst for synthesizing dimethyl carbonate, and preparation method and application thereof | |
| Parrino et al. | Formation of dibutyl carbonate and butylcarbamate via CO2 insertion in titanium (IV) butoxide and reaction with n-butylamine | |
| CN112745267B (en) | Imidazolyl ionic liquid and application thereof | |
| Ballivet‐Tkatchenko et al. | Synthesis of linear and cyclic carbonates | |
| KR101307559B1 (en) | Synthesis of glycerol carbonate using high active catalysts | |
| CN102285957B (en) | Method for preparing glycerol carbonate | |
| Wu et al. | Synthesis of dimethyl adipate from cyclopentanone and dimethyl carbonate over solid base catalysts | |
| CN107814782B (en) | Method for preparing 5-hydroxymethyl-2-furancarbonitrile by catalytic ammoxidation | |
| Juárez et al. | Activity of ceria and ceria-supported gold nanoparticles for the carbamoylation of aliphatic amines by dimethyl carbonate | |
| US9518035B2 (en) | Method for preparing glycidol using glycerol and glycidol obtained thereby | |
| Shanbhag et al. | Heterogeneous Catalysis for Chemical Fixation of CO 2 via Carbonylation Reactions | |
| Mariyaselvakumar et al. | Halogenated melamine formaldehyde polymers: Efficient, robust and cost-effective bifunctional catalysts for continuous production of cyclic carbonates via. CO2-epoxide cycloaddition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110921 |