CN102190601A - Method for synthesizing micromolecular alkyl carbamate - Google Patents
Method for synthesizing micromolecular alkyl carbamate Download PDFInfo
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- 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
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- urea
- carbamate
- separation system
- carbon dioxide
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- -1 alkyl carbamate Chemical compound 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004202 carbamide Substances 0.000 claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 150000003384 small molecules Chemical class 0.000 claims abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract 5
- 239000001099 ammonium carbonate Substances 0.000 claims abstract 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract 5
- 230000002745 absorbent Effects 0.000 claims abstract 2
- 239000002250 absorbent Substances 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- UMUXBDSQTCDPJZ-UHFFFAOYSA-N chromium titanium Chemical compound [Ti].[Cr] UMUXBDSQTCDPJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 4
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010926 purge Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 abstract 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 210000002700 urine Anatomy 0.000 abstract 1
- 235000011089 carbon dioxide Nutrition 0.000 description 18
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- SKKTUOZKZKCGTB-UHFFFAOYSA-N butyl carbamate Chemical compound CCCCOC(N)=O SKKTUOZKZKCGTB-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WQGANPAWGXQWCN-UHFFFAOYSA-N butyl carbamate butylcarbamic acid Chemical compound C(CCC)NC(O)=O.C(N)(OCCCC)=O WQGANPAWGXQWCN-UHFFFAOYSA-N 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XJFYWGIWEYQMPK-UHFFFAOYSA-N ethanol;urea Chemical compound CCO.NC(N)=O XJFYWGIWEYQMPK-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种合成小分子氨基甲酸烷基酯的方法。该方法使用一种釜式反应器与储气-冷凝-氨基甲酸铵/碳酸铵捕获器构成的反应分离系统，使用二氧化碳作为反应的副产物氨气的吸收剂，反应的促进剂和另外的羰基源，在醇尿素质量比为3/1-8/1，催化剂对尿质量比为0.01/1-0.2/1，反应温度为150-180℃，0.7-2.3MPa的二氧化碳的压力，反应时间为4-8小时的条件下，获得明显高于从尿素直接获得相应的氨基甲酸烷基酯的收率(100-108％，从尿素直接获得的氨基甲酸烷基酯的收率为90-96％)。并且，反应过程中产生的副产物氨气和少量的水与二氧化碳反应生成氨基甲酸铵或碳酸铵固体，可以起到及时移走副产物氨气效果的同时，大大减小反应器附带的储气罐的体积或免于氮气(或气态甲或乙醇)的吹扫，从而简化反应操作、降低生产成本。The invention relates to a method for synthesizing small molecule alkyl carbamate. The method uses a reaction separation system consisting of a tank reactor and a gas storage-condensation-ammonium carbamate/ammonium carbonate trap, using carbon dioxide as an absorbent for the by-product ammonia of the reaction, a reaction accelerator and another carbonyl source, the mass ratio of alcohol to urea is 3/1-8/1, the mass ratio of catalyst to urine is 0.01/1-0.2/1, the reaction temperature is 150-180°C, the pressure of carbon dioxide of 0.7-2.3MPa, and the reaction time is Under the condition of 4-8 hours, obtain obviously higher than directly obtain the yield (100-108%) of corresponding alkyl carbamate from urea, the yield of the alkyl carbamate directly obtained from urea is 90-96% ). Moreover, the by-product ammonia and a small amount of water produced during the reaction react with carbon dioxide to form ammonium carbamate or ammonium carbonate solid, which can remove the by-product ammonia in time and greatly reduce the gas storage attached to the reactor. The volume of the tank may be exempted from nitrogen (or gaseous formazan or ethanol) purging, thereby simplifying the reaction operation and reducing production costs.
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)
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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 |
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| 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 |
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2010
- 2010-03-11 CN CN200910221167XA patent/CN102190601A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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