CN112707815A - Method for coupling production of diphenyl carbonate and methyl phenylcarbamate - Google Patents
Method for coupling production of diphenyl carbonate and methyl phenylcarbamate Download PDFInfo
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- CN112707815A CN112707815A CN201911018998.7A CN201911018998A CN112707815A CN 112707815 A CN112707815 A CN 112707815A CN 201911018998 A CN201911018998 A CN 201911018998A CN 112707815 A CN112707815 A CN 112707815A
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- 238000000034 method Methods 0.000 title claims abstract description 67
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- IAGUPODHENSJEZ-UHFFFAOYSA-N methyl n-phenylcarbamate Chemical compound COC(=O)NC1=CC=CC=C1 IAGUPODHENSJEZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000010168 coupling process Methods 0.000 title claims abstract description 11
- 230000008878 coupling Effects 0.000 title claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 96
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 63
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 239000002815 homogeneous catalyst Substances 0.000 claims description 8
- 238000000066 reactive distillation Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- BSCCSDNZEIHXOK-UHFFFAOYSA-N phenyl carbamate Chemical compound NC(=O)OC1=CC=CC=C1 BSCCSDNZEIHXOK-UHFFFAOYSA-N 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 20
- 239000000178 monomer Substances 0.000 abstract description 14
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 41
- 239000000203 mixture Substances 0.000 description 21
- -1 Diaryl carbonate Chemical compound 0.000 description 13
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 9
- 239000004417 polycarbonate Substances 0.000 description 9
- 239000004246 zinc acetate Substances 0.000 description 9
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003671 uranium compounds Chemical group 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical class COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- OTSJRHVZRARHBC-UHFFFAOYSA-N benzylbenzene;carbamic acid Chemical compound NC(O)=O.NC(O)=O.C=1C=CC=CC=1CC1=CC=CC=C1 OTSJRHVZRARHBC-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- GUNDKLAGHABJDI-UHFFFAOYSA-N dimethyl carbonate;methanol Chemical compound OC.COC(=O)OC GUNDKLAGHABJDI-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
-
- 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
- C07C269/04—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 from amines with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for coupling production of diphenyl carbonate and methyl phenyl carbamate, which comprises the following steps: step A: mixing phenol, dimethyl carbonate and a first catalyst to obtain a mixed material, and feeding the mixed material into a diphenyl carbonate reaction rectifying tower to carry out a first reaction; and B: and the tower bottom product of the diphenyl carbonate reaction rectifying tower enters a diphenyl carbonate product separation tower, and the tower top product of the diphenyl carbonate reaction rectifying tower, the aniline and the second catalyst enter a methyl phenyl carbamate production reaction tower for a second reaction. The method of the invention directly enters the methanol and the dimethyl carbonate in the diphenyl carbonate reaction system into the polyurethane monomer methyl phenyl carbamate production reaction tower without separation, thereby improving the process efficiency, effectively increasing the raw material treatment capacity, saving the equipment investment and reducing the production cost.
Description
Technical Field
The invention relates to the technical field of coupling processes for producing polyester monomers, in particular to a method for coupling production of diphenyl carbonate and methyl phenylcarbamate.
Background
Diaryl carbonate is an important environmental protection chemical product, and can be used for synthesizing a plurality of important medicines, pesticides and other organic compounds and high molecular materials, such as aliphatic monoisocyanate, p-hydroxybenzoic acid polyester and the like. At present, diaryl carbonate is an important precursor for preparing polycarbonate by a melt transesterification method, and has great market prospect. The method for preparing polycarbonate by the melt transesterification method is a green process route, and compared with the traditional phosgene method, the method avoids the application of highly toxic raw materials and the treatment of toxic and harmful waste gas, and is a mainstream polycarbonate preparation process.
The diaryl carbonate (e.g., diphenyl carbonate) used in the melt process for the preparation of polycarbonate may be a monoarylhydroxy compound (e.g., phenol, methylphenol, dimethylphenol) and the dialkyl carbonate may be dimethyl carbonate or diethyl carbonate. The catalysts used in the transesterification process are reported in the literature to be mainly tin compounds (e.g., dibutyltin), titanium compounds (e.g., tetrabutyl titanate, etc.).
The diaryl carbonate synthesis process is reported more, wherein the synthesis method of the transesterification process route typically represents the following methods:
chinese patent CN1523005(a) reports an ester exchange process of reactive extractive distillation, which adopts a two-stage reaction process. In the feed proportioning, monoaryl hydroxyl compound and dialkyl carbonate with high molar ratio are added with catalyst from the top of the reaction tower, and dialkyl carbonate is fed into the tower kettle. Under the designed operation process, the excessive monoaryl hydroxyl compound is favorable to destroying the azeotropic system, raise the conversion rate of dialkyl carbonate and is favorable to extracting high purity low carbon alcohol.
European patents EP0780361 and EP0781760 report a reactive distillation process for the preparation of diaryl carbonates, such as diphenyl carbonate, using a pressurized continuous process. The raw material phenol and the catalyst enter from the top or the middle section of the reaction tower and react with the raw material dimethyl carbonate from the tower bottom. The mol ratio of dimethyl carbonate and phenol adopted in the reaction process is small, the main product after the reaction is methyl phenyl carbonate, and azeotrope extracted from the tower top enters an extraction separation system.
MDI (diphenylmethane diisocyanate) is a main raw material for preparing polyurethane elastomers, polyurethane rigid foams, semi-rigid foams and sizing agents, is also used for elastomers, adhesives, sealants, coatings and plastics, reaction injection molding products (automobile instrument panels and steering wheels) and the like, has excellent performance, is easy to store, and is the isocyanate with the largest yield and the widest application in the world at present. In order to solve the problems of the phosgene method MDI process, such as high toxicity, large potential safety hazard, strong corrosivity of byproduct hydrochloric acid, difficult removal of residual chlorine in the product, and the like, the production process of the non-phosgene method MDI is also actively developed. The first step is aminolysis of aniline and dimethyl carbonate to synthesize carbanilate (MPC), the second step is condensation of carbanilate and formaldehyde to synthesize diphenylmethane dicarbamate (MDC), and the third step is thermal decomposition of the product obtained by condensation to obtain MDI. Wherein the second and third steps are relatively easy to implement and the obtaining of MPC in the first step is critical to the overall process. The most promising methyl phenylcarbamate synthesis process is that the reaction of aniline and dimethyl carbonate is carried out under mild reaction conditions, is a liquid phase reaction, is a hotspot in the research of synthesizing MPC by a non-phosgene method at present, and is a potential route for realizing MPC industrialization. The method has mild reaction conditions, high atom utilization rate, no toxicity and no pollution, and the generated methanol can be recycled, and belongs to a clean production process.
Currently, few reports are made in the literature on the development of the process route, and mainly the screening of the catalyst is performed. The earlier adopted Lewis acid catalyst is uranium compound, William.F and other Lewis acids such as uranium compound and antimony compound are used as catalysts to synthesize IV-substituted methyl carbamate. Uranium dioxygen nitrate [ UO2(NO3)2] is used as a catalyst, reaction is carried out for 6 hours at 150 ℃, the yield of MPC is only 20.0%, the effect is not ideal, and besides, the uranium compound has reflective pollution and higher cost. Carbonates and alkoxides of alkali metals and alkaline earth metals and the like also show certain catalytic activity, are low in cost and are easy to prepare. The catalytic performance of Pd, Ti, Sn and Zn metal oxide catalysts on MPC synthesized by reacting dimethyl carbonate and aniline is examined by Combushiki et al, and the lead oxide activity is found to be the best. When the catalyst amount is 7.5%, the aniline conversion rate reaches 78%.
Disclosure of Invention
Aiming at the problems, the invention provides a coupling production process for coupling production of polycarbonate monomer diphenyl carbonate and polyurethane monomer methyl phenyl carbamate, which reduces the production cost of the process by adopting the comprehensive utilization of azeotropic products. Compared with the traditional process for producing diaryl carbonate by ester exchange, the method strengthens the reaction process, improves the process efficiency, can effectively increase the raw material treatment capacity, saves the equipment investment and reduces the production cost. The invention belongs to a continuous production process method and has good industrial practicability.
In a first aspect, the present invention provides a method for coupled production of diphenyl carbonate and methyl phenylcarbamate, comprising:
step A: mixing phenol, dimethyl carbonate and a first catalyst to obtain a mixed material, and feeding the mixed material into a diphenyl carbonate reaction rectifying tower to carry out a first reaction;
and B: and the tower bottom product of the diphenyl carbonate reaction rectifying tower enters a diphenyl carbonate product separation tower, and the tower top product of the diphenyl carbonate reaction rectifying tower, the aniline and the second catalyst enter a methyl phenyl carbamate production reaction tower for a second reaction.
According to some embodiments of the invention, the method further comprises step C: after the second reaction, the tower top product of the methyl phenyl carbamate production reaction tower enters an azeotropic system separation tower.
According to some embodiments of the invention, the top product of the diphenyl carbonate reactive rectification column comprises a dimethyl carbonate and methanol mixed component.
According to some embodiments of the invention, in step a, the molar ratio of phenol to dimethyl carbonate is (0.1-1): 1.
according to some embodiments of the invention, the first catalyst is selected from at least one of a tin-based homogeneous catalyst, a titanium-based homogeneous catalyst, a manganese-based homogeneous catalyst, and a zinc-based homogeneous catalyst.
According to some embodiments of the invention, the first catalyst is present in an amount of 0.1 to 5 wt% of the mixed feed.
According to some embodiments of the invention, the second catalyst is selected from at least one of a zinc-based catalyst, a bismuth-based catalyst, and a lead-based catalyst.
According to some embodiments of the invention, the second catalyst is present in an amount of 0.1 to 5 wt% of the mixed feed.
According to a preferred embodiment of the present invention, the second catalyst is selected from at least one of bismuth nitrate, lead nitrate and zinc acetate.
According to some embodiments of the present invention, the first reaction is carried out at a temperature of 150-,
according to some embodiments of the invention, the molar ratio of aniline to dimethyl carbonate in the second reaction is (1-15): 1.
according to a preferred embodiment of the invention, the molar ratio of aniline to dimethyl carbonate in the second reaction is (2-10: 1).
According to some embodiments of the invention, the temperature of the second reaction is between 50 ℃ and 200 ℃ and the pressure is between 0.1Mpa and 0.5 Mpa.
According to the method provided by the invention, the coupling method is a coupling production process of polycarbonate monomer diphenyl carbonate and polyurethane monomer methyl phenyl carbamate.
According to the invention, the first reaction isThe production process of polycarbonate monomer diphenyl carbonate comprises the steps of mixing phenol, dimethyl carbonate and a catalyst to obtain a mixed material, preheating the mixed material, then feeding the preheated mixed material into a diphenyl carbonate reaction rectifying tower for reaction, feeding a tower bottom product obtained after the reaction into a diphenyl carbonate product separation tower for separation, wherein the tower top product is a mixed component of dimethyl carbonate and methanol. The system equilibrium constant of the first reaction is smaller and reaches 10-6And therefore the system is very sensitive to methanol content. Therefore, a reaction rectification process is adopted, the conversion rate of phenol is greatly improved, the content of methanol in a dimethyl carbonate-methanol azeotropic system obtained by enrichment in the reaction process is less than 10 percent (generally about 5 percent), and the dimethyl carbonate is separated and recovered by the azeotropic system through an azeotropic separation process with high energy consumption for recycling the dimethyl carbonate.
According to the invention, the second reaction is a production process of polyurethane monomer methyl phenyl carbamate, and specifically comprises the steps of mixing a mixed component of dimethyl carbonate and methanol which are products at the top of a tower in the production process of diphenyl carbonate with aniline, then feeding the mixture into a methyl phenyl carbamate reaction tower for reaction, and feeding the product after the reaction into an azeotropic system separation tower for separation. The relatively high equilibrium constant of the second reaction, which theoretically gives an azeotropic composition with a high methanol content, means that the partial methanol content of the dimethyl carbonate feedstock to the reaction should have no significant effect on the reaction and product selectivity.
The diphenyl carbonate reaction system is sensitive to methanol, and the methanol and the dimethyl carbonate in the diphenyl carbonate reaction system directly enter a polyurethane monomer methyl phenyl carbamate production reaction tower without separation. The process efficiency is improved, the raw material treatment capacity can be effectively increased, the equipment investment is saved, and the production cost is reduced.
In a second aspect, the present invention provides a system for carrying out the method according to the first aspect, comprising a diphenyl carbonate reactive distillation unit, a diphenyl carbonate product separation unit, a methyl phenyl carbamate production reaction unit, wherein the bottom of the diphenyl carbonate reactive distillation unit is connected to the diphenyl carbonate product separation unit and the top of the diphenyl carbonate reactive distillation unit is connected to the methyl phenyl carbamate production reaction unit.
According to some embodiments of the present invention, the diphenyl carbonate reactive rectification unit comprises a diphenyl carbonate reactive rectification column and a heat exchanger.
According to some embodiments of the present invention, the diphenyl carbonate product separation unit comprises a diphenyl carbonate product separation column and a heat exchanger.
According to some embodiments of the invention, the system further comprises an azeotropic system separation unit connected to the top of the methyl phenyl carbamate production reaction unit.
According to some embodiments of the invention, the methyl phenyl carbamate production reaction unit comprises a methyl phenyl carbamate production reaction column and a heat exchanger.
In a third aspect, the present invention provides a use of a method according to the first aspect or a system according to the second aspect for the coupled production of diphenyl carbonate and methyl phenylcarbamate.
The production process for coupling production of polycarbonate monomer diphenyl carbonate and polyurethane monomer methyl phenyl carbamate provided by the invention reduces the production cost of the process by comprehensive utilization of azeotropic products. The invention is characterized in that the reaction process system comprises a polycarbonate monomer diphenyl carbonate reaction rectification unit, a product separation unit, a polyurethane monomer methyl phenyl carbamate reaction unit and an azeotropic component separation unit. In the reaction process, the mixed product component of dimethyl carbonate and methanol enters a polyurethane monomer methyl phenyl carbamate reaction unit. Compared with the traditional process for producing diaryl carbonate by ester exchange, the method strengthens the reaction process, improves the process efficiency, can effectively increase the raw material treatment capacity, saves the equipment investment and reduces the production cost. The invention belongs to a continuous production process method and has good industrial practicability.
Drawings
Fig. 1 is a flow diagram of a coupled process for the production of diphenyl carbonate and methyl phenylcarbamate according to the present invention. In the figure, T101 is a diphenyl carbonate reaction rectifying tower, T102 is a diphenyl carbonate product separating tower, T103 is a methyl phenylcarbamate reaction tower, P1-P6 are transfer pumps, E is a heat exchanger, V1 is a dimethyl carbonate raw material tank, V2 is a phenol raw material tank, and V3 is an aniline raw material tank.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Example 1
The process flow shown in FIG. 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as 1, the content of tetraphenyl titanate as 0.5 percent as an example, the reaction temperature is 180 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 1. The dimethyl carbonate feed tank from V1 with a flow rate of 900kg/h enters column T101 from P1; the flow rate of a phenol raw material tank from V2 is 900kg/h, the feeding temperature is 160 ℃, the material flow rate at the bottom outlet of a tower T101 is 992kg/h, the composition is 4.64 wt% of diphenyl carbonate, 22.8 wt% of methyl phenyl carbonate, 72.7 wt% of phenol, the flow rate at the top of the tower T101 is 808.3kg/h, the composition is 92.2% of dimethyl carbonate and 7.56% of methanol, the condensed product enters T103 through a material pump P4, aniline from V3 enters T103 at 93.54kg/h, the outlet flow rate is 904.8kg/h, the content of the product, namely methyl phenylamate, is 16.7 wt%, the content of aniline is 0.3 wt%, the content of dimethyl carbonate is 72.4 wt% and the content of methanol is 10.3 wt% after reaction at the reaction temperature of 160 ℃, the pressure of 0.5MPa and the content of zinc acetate is 0.5.
Example 2
The process flow shown in FIG. 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as 1, the content of tetraphenyl titanate as 0.5 percent as an example, the reaction temperature is 185 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 1. The dimethyl carbonate feed tank from V1 with a flow rate of 900kg/h enters column T101 from P1; the flow rate of a phenol raw material tank from V2 is 900kg/h, the feeding temperature is 160 ℃, the material flow rate at the bottom outlet of a tower T101 is 800kg/h, the composition is 6.2 wt% of diphenyl carbonate, 24.2 wt% of methyl phenyl carbonate, 69.6 wt% of phenol, the flow rate at the top of the tower T101 is 800.0kg/h, the composition is 91.3% of dimethyl carbonate and 8.7% of methanol, the condensed diphenyl carbonate enters T103 through a material pump P4, aniline from V3 enters T103 at 94.4kg/h, the outlet flow rate is 894.4kg/h, the content of the product, namely methyl phenylcarbamate, is 16.5 wt%, the content of aniline is 0.4 wt%, the content of dimethyl carbonate is 71.8 wt% and the content of methanol is 11.3 wt% after reaction at the reaction temperature of 160 ℃, the pressure of 0.5MPa and the content of zinc acetate is 0..
Example 3
The process flow shown in FIG. 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as 1, the content of tetraphenyl titanate as 0.5 percent as an example, the reaction temperature is 185 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 2. The dimethyl carbonate feed tank from V1 with a flow rate of 900kg/h enters column T101 from P1; the flow rate of a phenol raw material tank from V2 is 900kg/h, the feeding temperature is 170 ℃, the material flow rate at the bottom outlet of a tower T101 is 1021.5kg/h, the composition is 5.85 wt% of diphenyl carbonate, 29.3 wt% of methyl phenyl carbonate, 64.8 wt% of phenol, the flow rate at the top of the tower T101 is 778.5kg/h, the composition is 89.6% of dimethyl carbonate and 10.4% of methanol, the condensed product enters T103 through a material pump P4, aniline from V3 enters T103 at 90.2kg/h, the outlet flow rate is 868.7kg/h after reaction at the reaction temperature of 150 ℃, the pressure of 0.5MPa and the content of zinc acetate is 1%, the content of the product of methyl phenylamate is 16.5 wt%, the aniline is 0.2 wt%, the dimethyl carbonate is 70.5 wt%, and the methanol is 12.8 wt%.
Example 4
The process flow shown in FIG. 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as an example, 0.75, the content of tetraphenyl titanate as an example, the reaction temperature is 180 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 1. The dimethyl carbonate feed tank from V1 with a flow rate of 1200kg/h enters column T101 from P1; the flow rate of a phenol raw material tank from V2 is 900kg/h, the feeding temperature is 170 ℃, the material flow rate at the bottom outlet of a tower T101 is 1018.0kg/h, the composition is 5.64 wt% of diphenyl carbonate, 28.6 wt% of methyl phenyl carbonate, 65.8 wt% of phenol, the flow rate at the top of the tower T101 is 1082.0kg/h, the composition is 82.8% of dimethyl carbonate and 7.2% of methanol, the condensed product enters T103 through a material pump P4, aniline from V3 enters T103 at 129.4kg/h, the outlet flow rate is 1211.4kg/h after the reaction is carried out at the reaction temperature of 150 ℃, the pressure of 0.5MPa and the zinc acetate content of 1%, the product is 16.9 wt%, 0.3 wt% of aniline, 72.8 wt% of dimethyl carbonate and 10.0 wt% of methanol.
Example 5
The process flow shown in FIG. 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as an example, 0.75, the content of tetraphenyl titanate as an example, the reaction temperature is 180 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 2. The dimethyl carbonate feed tank from V1 with a flow rate of 1200kg/h enters column T101 from P1; the flow rate of a phenol raw material tank from V2 is 900kg/h, the feeding temperature is 170 ℃, the material flow rate at the bottom outlet of a tower T101 is 1037.5kg/h, the composition is diphenyl carbonate 6.4 wt%, methyl phenyl carbonate 32.7 wt%, phenol 60.9 wt%, the flow rate at the top of the tower T101 is 1062.4kg/h, the composition is dimethyl carbonate 91.4%, methanol is 8.6%, after condensation, the condensed product enters T103 through a material pump P4, aniline from V3 enters T103 at 125.5kg/h, the outlet flow rate is 1188.0kg/h after reaction at the reaction temperature of 150 ℃, the pressure of 0.5MPa and the bismuth nitrate content of 1%, the product is methyl phenylamate content of 16.9 wt%, aniline content of 0.2 wt%, dimethyl carbonate is 71.7 wt%, and methanol is 11.3 wt%.
Example 6
The process flow shown in FIG. 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as 1, the content of tetraphenyl titanate as 0.2 percent as an example, the reaction temperature is 175 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 1. The dimethyl carbonate feed tank from V1 with a flow rate of 900kg/h enters column T101 from P1; the flow rate of a phenol raw material tank from V2 is 900kg/h, the feeding temperature is 170 ℃, the material flow rate at the bottom outlet of a tower T101 is 965.6kg/h, the composition is 3.4 wt% of diphenyl carbonate, 19.0 wt% of methyl phenyl carbonate, 77.6 wt% of phenol, the flow rate at the top of the tower T101 is 833.9kg/h, the composition is 94.2% of dimethyl carbonate and 5.8% of methanol, the condensed product enters T103 through a material pump P4, aniline from V3 enters T103 at 101.5kg/h, the outlet flow rate is 935.4kg/h after the reaction is carried out at the reaction temperature of 150 ℃, the pressure of 0.5MPa and the content of zinc acetate is 1%, the content of the product of methyl phenylcarbamate is 17.1 wt%, the content of aniline is 0.3 wt%, the content of dimethyl carbonate is 73.8 wt%, and the content of methanol is 9.0.
Example 7
The process flow shown in FIG. 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as 1, the content of tetraphenyl titanate as 0.2 percent as an example, the reaction temperature is 180 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 1. The dimethyl carbonate feed tank from V1 with a flow rate of 900kg/h enters column T101 from P1; the flow rate of a phenol raw material tank from V2 is 900kg/h, the feeding temperature is 170 ℃, the material flow rate at the bottom outlet of a tower T101 is 987.0kg/h, the composition is diphenyl carbonate 4.2 wt%, methyl phenyl carbonate 21.7 wt%, phenol 74.0 wt%, the flow rate at the top of the tower T101 is 813.0kg/h, the composition is dimethyl carbonate 92.9%, methanol is 7.1%, after condensation, the condensed product enters T103 through a material pump P4, aniline from V3 enters T103 at 97.6kg/h, the outlet flow rate is 910.6kg/h after reaction at the reaction temperature of 150 ℃, the pressure of 0.5MPa and the zinc acetate content of 1%, the content of the product, namely methyl phenylcarbamate, is 16.9 wt%, the aniline is 0.3 wt%, the dimethyl carbonate is 72.9 wt%, and the methanol is 9.9 wt%.
Comparative example 1
The process flow shown in FIG. 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as 1, the content of tetraphenyl titanate as 0.5 percent as an example, the reaction temperature is 180 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 1. The dimethyl carbonate feed tank from V1, which contains 1% methanol and has a flow rate of 900kg/h, enters column T101 from P1; the flow rate of a phenol raw material tank from V2 was 900kg/h, the feed temperature was 160 ℃, the flow rate of a material at the bottom outlet was 908.32kg/h, the composition was 0.89 wt% of diphenyl carbonate, 3.54 wt% of methyl phenyl carbonate, 95.57 wt% of phenol, the flow rate at the top was 881.68kg/h, the composition was 98.6% of dimethyl carbonate, and the composition was 1.4% of methanol. After condensation, a material pump P4 enters T103, aniline from V3 enters T103 at 85.81kg/h, after reaction at 160 ℃, the pressure of 0.5MPa and the content of zinc acetate is 0.5 percent, the outlet flow rate is 137.82kg/h, the content of the product, namely methyl phenylcarbamate, is 14.0 percent by weight, aniline is 0.3 percent by weight, dimethyl carbonate is 74.7 percent by weight, and methanol is 11.0 percent by weight.
Comparative example 2
The process flow shown in the attached figure 1 is adopted, taking the molar ratio of phenol to dimethyl carbonate as 1, the content of tetraphenyl titanate as 0.5 percent as an example, the reaction temperature is 180 ℃, the reaction pressure is 0.1MPa, and the reflux ratio is 1. The dimethyl carbonate feed tank from V1 with a flow rate of 900kg/h enters column T101 from P1; the phenol raw material tank flow from V2 is 900kg/h, the feeding temperature is 160 ℃, the material flow at the bottom outlet is 991.66kg/h, the composition is diphenyl carbonate 4.6 wt%, methyl phenyl carbonate 22.8 wt%, phenol 72.6 wt%, the top flow is 808.3kg/h, the composition is dimethyl carbonate 92.4%, methanol is 7.58%, after condensation, the condensed product directly enters the outlet5 for separation and purification through a material pump P4. Aniline from V3 entered T103 at 85.81kg/h, dimethyl carbonate from V1 entered T103 at 747kg/h, after reaction at 160 ℃, pressure 0.5MPa, zinc acetate content 0.5%, outlet flow rate was 832.8kg/h, product methyl phenylcarbamate content was 15.9 wt%, aniline 0.5 wt%, dimethyl carbonate was 74.9%, methanol was 8.7%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for coupling production of diphenyl carbonate and methyl phenyl carbamate, comprising:
step A: mixing phenol, dimethyl carbonate and a first catalyst to obtain a mixed material, and feeding the mixed material into a diphenyl carbonate reaction rectifying tower to carry out a first reaction;
and B: and the tower bottom product of the diphenyl carbonate reaction rectifying tower enters a diphenyl carbonate product separation tower, and the tower top product of the diphenyl carbonate reaction rectifying tower, the aniline and the second catalyst enter a methyl phenyl carbamate production reaction tower for a second reaction.
2. The method according to claim 1, characterized in that it further comprises a step C: after the second reaction, the tower top product of the methyl phenyl carbamate production reaction tower enters an azeotropic system separation tower.
3. The method of claim 1 or 2, wherein the top product of the diphenyl carbonate reactive distillation column comprises a mixed component of dimethyl carbonate and methanol.
4. The process of any one of claims 1 to 3, wherein in step A, the molar ratio of phenol to dimethyl carbonate is (0.1 to 1): 1.
5. the method according to any one of claims 1 to 4, wherein the first catalyst is selected from at least one of a tin-based homogeneous catalyst, a titanium-based homogeneous catalyst, a manganese-based homogeneous catalyst and a zinc-based homogeneous catalyst, preferably the first catalyst is present in an amount of 0.1 to 5 wt.% of the mixed material; and/or the second catalyst is at least one selected from a zinc-based catalyst, a bismuth-based catalyst and a lead-based catalyst, and preferably, the content of the second catalyst is 0.1-5 wt% of the mixed material.
6. The process of any one of claims 1 to 5, wherein in the second reaction, the molar ratio of aniline to dimethyl carbonate is (1-15): 1, preferably (2-10: 1).
7. The method as claimed in any one of claims 1 to 6, wherein the temperature of the first reaction is 150 ℃ and 200 ℃, the pressure is 0.1 to 0.5MPa, and the reflux ratio is 0.4 to 3; and/or the temperature of the second reaction is 50-200 ℃ and the pressure is 0.1-0.5 Mpa.
8. A system for carrying out the method according to any one of claims 1 to 7, comprising a diphenyl carbonate reactive rectification unit, a diphenyl carbonate product separation unit, a phenyl carbamate production reaction unit, wherein the bottom of the diphenyl carbonate reactive rectification unit is connected to the diphenyl carbonate product separation unit and the top of the diphenyl carbonate reactive rectification unit is connected to the phenyl carbamate production reaction unit,
preferably, the diphenyl carbonate reaction rectification unit comprises a diphenyl carbonate reaction rectification column and a heat exchanger, and the diphenyl carbonate product separation unit comprises a diphenyl carbonate product separation column and a heat exchanger.
9. The system of claim 8, further comprising an azeotropic system separation unit connected to the top of the methyl phenyl carbamate production reaction unit, preferably the methyl phenyl carbamate production reaction unit comprises a methyl phenyl carbamate production reaction tower and a heat exchanger.
10. Use of the method according to any one of claims 1 to 7 or the system according to claim 8 or 9 for the coupled production of diphenyl carbonate and methyl phenylcarbamate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113979840A (en) * | 2021-11-29 | 2022-01-28 | 中国成达工程有限公司 | Three-tower differential pressure thermal coupling rectification method for separating methanol, dimethyl carbonate and phenol |
| CN115260033A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Method for preparing diphenyl carbonate and obtained diphenyl carbonate |
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| CN102134205A (en) * | 2010-01-25 | 2011-07-27 | 湖南大学 | Method for preparing carbamate |
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| CN115260033A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Method for preparing diphenyl carbonate and obtained diphenyl carbonate |
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