CN112898184A - Method for continuously synthesizing alicyclic carbamate - Google Patents
Method for continuously synthesizing alicyclic carbamate Download PDFInfo
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- CN112898184A CN112898184A CN202110096388.XA CN202110096388A CN112898184A CN 112898184 A CN112898184 A CN 112898184A CN 202110096388 A CN202110096388 A CN 202110096388A CN 112898184 A CN112898184 A CN 112898184A
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- carbamate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—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 by reactions not involving the formation of carbamate groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention relates to a method for continuously synthesizing alicyclic carbamate. The method comprises the following steps: preheating a raw material gas and a raw material liquid to 20-130 ℃ through a preheater, introducing the raw material gas and the raw material liquid into a fixed bed reactor filled with a supported metal catalyst, and reacting at 30-150 ℃ and under the reaction pressure of 0-5 MPa to obtain alicyclic carbamate; the supported metal catalyst comprises the following components: the active component metal salt is rhodium active component metal salt. The invention has the advantages of high mass and heat transfer efficiency, short reaction time, high product selectivity, intrinsic safety, high space-time efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of organic compound production, and particularly relates to a green and intrinsically safe production method for continuously synthesizing alicyclic carbamate serving as a raw material intermediate for high-grade polyurethane synthesis by using a fixed bed reactor.
Background
Cycloaliphatic isocyanates are a special class of chemicals having a-N ═ C ═ O functionality, for example, methylcyclohexyl diisocyanate (HTDI), dicyclohexylmethane diisocyanate (H)12MDI), and the like are alicyclic diisocyanates of the non-yellow modification. Because the benzene ring is substituted by the hexatomic aliphatic ring, unsaturated double bonds do not exist, the polyurethane product prepared by the method has the excellent characteristics of light stability, no yellowing, light stability, weather resistance, high mechanical property and the like, and is a core raw material for producing high-grade polyurethane. Compared with aromatic isocyanate TDI, MDI and the like, the alicyclic isocyanate has more excellent performance and lower toxicity, and is mainly used for the production of high-end or special polyurethane products.
The alicyclic carbamate is an intermediate of a green and safe process for synthesizing the alicyclic isocyanate. Typically by catalytic hydrogenation of aromatic ring carbamates. There are two main types of catalysts: one kind is noble metal with Ru, Rh, Pd as active component, the other kind is non-noble metal catalyst with Ni as active component; the carrier comprises alumina, activated carbon, magnesia, carbon nano tube, titanium oxide, zinc-magnesium-aluminum composite oxide (Zn-Mg-Al-O) and modification of the carrier (chemical industry and engineering, 2019,36(5): 25-30); the reaction device mainly comprises a kettle type batch reactor. However, a tank batch reactor exists: the mixing effect of reactants is poor, and the danger of local overheating is generated; the loading and unloading process is time-consuming, and the production efficiency is low; the concentration of the catalyst is relatively low, and the reaction rate is slow; the side reaction is easy to occur when the product stays in the reactor all the time.
Due to the reasons of long reaction time, pipeline blockage caused by precipitation of solid reactants and the like caused by low reaction rate of the catalyst, no report of the reaction for synthesizing alicyclic carbamate by continuously hydrogenating aromatic carbamate in a fixed bed reactor is found at present.
Disclosure of Invention
The invention aims to provide a method for continuously synthesizing alicyclic carbamate, aiming at overcoming the defects in the prior art. The method adopts the fixed bed reactor to continuously hydrogenate the aromatic carbamate to synthesize the alicyclic carbamate, avoids the defects of poor reactant mixing effect, long time consumption, low efficiency and the like of a kettle type reactor operated intermittently, and has the advantages of high mass and heat transfer efficiency, short reaction time, high product selectivity, intrinsic safety, high space-time efficiency and the like.
The technical scheme of the invention is as follows:
a process for the continuous synthesis of cycloaliphatic carbamates which comprises the steps of:
preheating a raw material gas and a raw material liquid to 20-130 ℃ through a preheater, simultaneously introducing the raw material gas and the raw material liquid into a fixed bed reactor filled with a supported metal catalyst, and reacting at 30-150 ℃ and under the reaction pressure of 0-5 MPa to obtain alicyclic carbamate;
wherein the airspeed of the raw material gas is 900-3000 h-1And the liquid hourly space velocity is 3-15 h-1The raw material liquid is a mixed liquid of aromatic carbamate and a solvent; the molar ratio is aromatic carbamate: the solvent is 1: 10-1: 500; the feed gas is hydrogen.
The supported metal catalyst has a particle size of 20-40 meshes, and comprises the following components: active component metal salt and a carrier, wherein the metal salt loading amount calculated by the active component is 0.1-10% by mass percentage; the catalyst and the quartz sand are mixed in the same particle size and volume ratio and then placed in a reactor.
The active component metal salt is rhodium active component metal salt. Preferably one or more of rhodium trichloride, rhodium nitrate and rhodium acetate.
The carrier is Al2O3、TiO2、SiO2、ZrO2、MgO、ZnO、Fe2O3And aluminosilicate, preferably Al2O3。
The concentration of the active component metal salt is preferably 1-5% (preferably 3-5%) by mass percent.
The aromatic carbamate is one or more of phenyl carbamate, toluene dicarbamate and 4, 4' -diphenylmethane dicarbamate.
The phenyl carbamate is selected from one or more of methyl phenyl carbamate, ethyl phenyl carbamate, propyl phenyl carbamate, butyl phenyl carbamate, pentyl phenyl carbamate, hexyl phenyl carbamate, heptyl phenyl carbamate, octyl phenyl carbamate, nonyl phenyl carbamate and decyl phenyl carbamate;
the toluenedicarbamic acid ester is selected from one or more of toluenediurethane, toluenediurethane propyl ester, toluenediurethane butyl ester, toluenediurethane pentyl ester, toluenediurethane hexyl ester, toluenediurethane heptyl ester, toluenediurethane octyl ester, toluenediurethane nonyl ester and toluenediurethane decyl ester;
the 4,4 ' -diphenylmethane dicarbamic acid ester is selected from one or more of methyl 4,4 ' -diphenylmethane dicarbamic acid, ethyl 4,4 ' -diphenylmethane dicarbamic acid, propyl 4,4 ' -diphenylmethane dicarbamic acid, butyl 4,4 ' -diphenylmethane dicarbamic acid, pentyl 4,4 ' -diphenylmethane dicarbamic acid, hexyl 4,4 ' -diphenylmethane dicarbamic acid, heptyl 4,4 ' -diphenylmethane dicarbamic acid, octyl 4,4 ' -diphenylmethane dicarbamic acid, nonyl 4,4 ' -diphenylmethane dicarbamic acid, and decyl 4,4 ' -diphenylmethane dicarbamic acid.
The solvent is at least one of alkane, aromatic hydrocarbon, cyclane, ether, ester, amine and sulfone. The solvent is one or more of liquid paraffin, nitrobenzene, o-nitrotoluene, tetrahydrofuran, diphenyl ether, methyl acetate, dimethyl carbonate, diisooctyl phthalate, dioctyl sebacate, dimethyl phthalate, dibutyl phthalate, N-dimethylacetamide and dimethyl sulfoxide.
The solvent is preferably one or more of methyl acetate, dimethyl carbonate, N-dimethylacetamide, diisooctyl phthalate, dioctyl sebacate, dimethyl phthalate or dibutyl phthalate.
The temperature of the preheater is preferably 40-80 ℃.
The temperature of the reactor is preferably 60-100 ℃.
The reaction pressure is preferably 1-3 MPa.
The molar ratio is preferably an aromatic carbamate: the solvent is 1: 30-1: 300.
The invention has the beneficial effects that:
the invention firstly provides the synthesis of alicyclic carbamate by continuously hydrogenating aromatic carbamate by using a fixed bed. The invention adopts continuous flow, compared with a kettle type reactor, the gas-liquid mixing effect is increased, and the reaction time is reduced (the fixed bed only needs 4-20 min to reach 100 percent yield, while the kettle type reactor needs at least 66 min).
The method has the advantages of simple process, mild reaction conditions, convenient and continuous operation, and green and intrinsic safety characteristics. The product yield can reach 100 percent, the selectivity is close to or 100 percent, and the method has obvious social and economic benefits and is suitable for industrial production.
Detailed Description
The present invention is illustrated by the following examples, but is not limited thereto.
Example 1:
preparing a catalyst: preparing 5% Rh/gamma-Al by adopting equal-volume impregnation method2O3A catalyst. 0.410g of RhCl is added3·xH2Dissolving O in 8mL of anhydrous methanol, and weighing 3g of gamma-Al2O3Soaking in the above solution, drying, calcining, and reducing to obtain 5% Rh/gamma-Al2O3。
And (3) uniformly mixing 2mL of catalyst with the particle size of 20-40 meshes and quartz sand, and placing the mixture in a tubular fixed bed reactor with the inner diameter of 10mm and the length of 600 mm. Feed gas H2And raw material liquid (methyl phenyl carbamate: methyl acetate: 1:30) introduced by a plunger pump are mixed and enter a preheater for preheating, and then enter a reactor bed layer for reaction. Wherein the temperature of the preheater is 45 ℃, the temperature of the reactor is 60 ℃, the reaction pressure is 1MPa, and H is2Airspeed of 900h-1(30mL/min)，Space velocity of raw material liquid is 6h-1(0.2 mL/min). And then condensing by a condenser, and carrying out gas-liquid separation to obtain the product methyl cyclohexylcarbamate.
The product is analyzed by gas chromatography, when the operation time is 4 hours, the conversion rate can reach 100 percent, the selectivity of the cyclohexyl methyl carbamate is 100 percent, and the activity is not obviously reduced within 10 hours of reaction.
Example 2:
preparing a catalyst: the same as in example 1.
The space velocity of the raw material liquid in the reaction process is 6h-1Increased to 15h-1Otherwise, the procedure of example 1 was repeated.
The product was analyzed by gas chromatography, the conversion of methyl phenylcarbamate gradually decreased from 100% with the running time, and 94.17% at 10h of reaction, but the selectivity of methyl cyclohexylcarbamate was 100%.
Example 3:
preparing a catalyst: 1% Rh/gamma-Al is prepared by adopting an isometric immersion method2O3A catalyst. 0.079g of RhCl is added3·xH2Dissolving O in 8mL of anhydrous methanol, and weighing 3g of gamma-Al2O3Soaking in the solution, drying, calcining, and reducing to obtain 1% Rh/gamma-Al2O3。
The procedure is as in example 2.
The product is analyzed by gas chromatography, the conversion rate of the methyl phenyl carbamate is rapidly reduced from 100 percent along with the running time, the reaction time is only 2.78 percent when the reaction lasts for 10 hours, but the selectivity of the methyl cyclohexyl carbamate is 100 percent.
Example 4:
preparing a catalyst: the same as in example 1.
The reaction process comprises the following steps of: the same procedure as in example 2 was repeated except that the molar ratio of methyl acetate to methyl acetate was changed to 1:20 (1: 30).
The product is analyzed by gas chromatography, the conversion rate of the methyl phenyl carbamate is gradually reduced from 99.44% along with the running time, the conversion rate is reduced to 75.28% when the reaction is carried out for 10 hours, but the selectivity of the methyl cyclohexyl carbamate is 100%.
Example 5:
preparing a catalyst: the same as in example 1.
The reaction was carried out in the same manner as in example 4 except that the preheater temperature was adjusted to 60 ℃ and the reactor temperature was adjusted to 80 ℃.
The product is analyzed by gas chromatography, the conversion rate of the methyl phenyl carbamate is gradually reduced from 99.92 percent along with the running time, the conversion rate is reduced to 82.65 percent when the reaction is carried out for 10 hours, but the selectivity of the methyl cyclohexyl carbamate is 100 percent.
Example 6:
preparing a catalyst: 3% Rh/gamma-Al is prepared by adopting an isometric immersion method2O3A catalyst. 0.241g of RhCl was added3·xH2Dissolving O in 8mL of anhydrous methanol, and weighing 3g of gamma-Al2O3Soaking in the solution, drying, calcining, and reducing to obtain 1% Rh/gamma-Al2O3。
The procedure is as in example 5.
The product is analyzed by gas chromatography, the conversion rate of the methyl phenyl carbamate is reduced rapidly from 100 percent along with the running time, the conversion rate is reduced to 25.47 percent when the reaction is carried out for 10 hours, but the selectivity of the methyl cyclohexyl carbamate is 100 percent.
Example 7:
preparing a catalyst: the same as in example 1.
And (3) uniformly mixing 2mL of catalyst with the particle size of 20-40 meshes and quartz sand, and placing the mixture in a tubular fixed bed reactor with the inner diameter of 10mm and the length of 600 mm. Feed gas H2And raw material liquid (toluene dicarbamate: methyl acetate: 1:120 in molar ratio) introduced by a plunger pump are mixed, enter a preheater for preheating, and then enter a reactor bed layer for reaction. The temperature of the preheater is 40 ℃, the temperature of the reactor is 60 ℃, the reaction pressure is 1MPa, and H is2Airspeed of 900h-1Space velocity of raw material liquid of 9h-1. And then condensing by a condenser, and carrying out gas-liquid separation to obtain a product methyl cyclohexyl carbamate.
The product is analyzed by liquid chromatography, when the operation time is 2 hours, the conversion rate can reach 100 percent, the methyl methylcyclohexyl carbamate selectivity is 100 percent, and the activity is not obviously reduced within 10 hours of reaction.
Example 8:
except that the catalyst is 5 percent Rh/gamma-Al2O3Changed to 1% Rh/gamma-Al2O3Otherwise, the procedure was as in example 7.
The product was analyzed by liquid chromatography with a 1h on stream conversion of 76.01% and methyl methylcyclohexyl carbamate selectivity of 100%. The conversion rate decreased rapidly with the running time, and at 9h of reaction time, the conversion rate was only 0.5%, but the selectivity was still 100%.
Example 9:
preparing a catalyst: the same as in example 1.
And (3) uniformly mixing 2mL of catalyst with the particle size of 20-40 meshes and quartz sand, and placing the mixture in a tubular fixed bed reactor with the inner diameter of 10mm and the length of 600 mm. Feed gas H2And raw material liquid (the molar ratio of 4, 4' -diphenylmethane diamino methyl formate: methyl acetate is 1:250) introduced by a plunger pump are mixed, enter a preheater for preheating, and then enter a reactor bed layer for reaction. Wherein the temperature of the preheater is 60 ℃, the temperature of the reactor is 80 ℃, the reaction pressure is 1MPa, and H is2Space velocity of 1200h-1Space velocity of raw material liquid of 9h-1. And then condensing by a condenser, and carrying out gas-liquid separation to obtain the product 4, 4' -dicyclohexylmethane diamino methyl formate.
The product is analyzed by liquid chromatography, when the running time is 3 hours, the conversion rate is 99.23 percent, the selectivity of 4, 4' -dicyclohexyl methane diamino methyl formate is 91.02 percent, and the activity is not obviously reduced within 10 hours of reaction.
Example 10:
preparing a catalyst: the same as in example 1.
During the reaction, the raw material liquid, 4' -diphenylmethane diamino methyl formate: the same procedure as in example 9 was repeated except that the molar ratio of methyl acetate to methyl acetate was changed to 1: 300.
The product is analyzed by liquid chromatography, when the operation time is 4 hours, the conversion rate can reach 100 percent, the selectivity of 4, 4' -dicyclohexyl methane diamino methyl formate is 92.33 percent, and the activity is not obviously reduced within 10 hours of reaction.
Example 11:
preparing a catalyst: the same as in example 1.
The reaction procedure was carried out in the same manner as in example 10 except that the preheater temperature was adjusted to 60 ℃ and the reactor temperature was adjusted to 80 ℃ in the reaction procedure.
The product is analyzed by liquid chromatography, when the running time is 3 hours, the conversion rate can reach 100 percent, the selectivity of 4,4 '-dicyclohexyl methane diamino methyl formate is 92.33 percent, the conversion rate keeps 100 percent along with the running time, but the selectivity of the 4, 4' -dicyclohexyl methane diamino methyl formate is reduced to 86.99 percent when the running time is 10 hours.
As can be seen from the above examples, the present invention provides a synthesis method in a continuous flow fixed bed reactor, which addresses the deficiencies of the batch tank reactor synthesis of cycloaliphatic carbamates. The alicyclic carbamate is synthesized by continuously hydrogenating the aromatic carbamate on the fixed bed reactor, and the method has the advantages of high mass transfer and heat transfer efficiency, short reaction time, high product selectivity, intrinsic safety, high space-time efficiency and the like.
The invention is not the best known technology.
Claims (10)
1. A continuous synthesis process of alicyclic carbamates, characterized in that it comprises the following steps:
preheating a raw material gas and a raw material liquid to 20-130 ℃ through a preheater, simultaneously introducing the raw material gas and the raw material liquid into a fixed bed reactor filled with a supported metal catalyst, and reacting at 30-150 ℃ and under the reaction pressure of 0-5 MPa to obtain alicyclic carbamate;
wherein the airspeed of the raw material gas is 900-3000 h-1And the liquid hourly space velocity is 3-15 h-1The raw material liquid is a mixed liquid of aromatic carbamate and a solvent; the molar ratio is aromatic carbamate: the solvent is 1: 10-1: 500; the raw material gas is hydrogen;
the supported metal catalyst has a particle size of 20-40 meshes, and comprises the following components: the active component metal salt and a carrier, wherein the loading amount of the active component metal salt is 0.1-10% by mass percent; mixing the catalyst and quartz sand with the same particle size and equal volume ratio, and placing the mixture in a reactor;
the solvent is one or more of alkane, aromatic hydrocarbon, cyclane, ether, ester, amine and sulfone;
the active component metal salt is rhodium active component metal salt;
the aromatic carbamate is one or more of phenyl carbamate, toluene dicarbamate and 4, 4' -diphenylmethane dicarbamate;
the carrier is Al2O3、TiO2、SiO2、ZrO2、MgO、ZnO、Fe2O3And aluminosilicate, etc.
2. The continuous process for the synthesis of alicyclic urethanes according to claim 1, wherein said support is preferably Al2O3。
3. The method for continuously synthesizing alicyclic urethane according to claim 1, wherein the loading amount of the active component metal salt is preferably 3 to 5% by mass.
4. The method for continuously synthesizing alicyclic carbamate according to claim 1, wherein the active component metal salt is preferably one or more of rhodium trichloride, rhodium nitrate and rhodium acetate.
5. The continuous method according to claim 1, wherein the phenyl carbamate is selected from one or more of methyl phenyl carbamate, ethyl phenyl carbamate, propyl phenyl carbamate, butyl phenyl carbamate, pentyl phenyl carbamate, hexyl phenyl carbamate, heptyl phenyl carbamate, octyl phenyl carbamate, nonyl phenyl carbamate, decyl phenyl carbamate;
the toluenedicarbamic acid ester is selected from one or more of toluenediurethane, toluenediurethane propyl ester, toluenediurethane butyl ester, toluenediurethane pentyl ester, toluenediurethane hexyl ester, toluenediurethane heptyl ester, toluenediurethane octyl ester, toluenediurethane nonyl ester and toluenediurethane decyl ester;
the 4,4 ' -diphenylmethane dicarbamic acid ester is selected from one or more of methyl 4,4 ' -diphenylmethane dicarbamic acid, ethyl 4,4 ' -diphenylmethane dicarbamic acid, propyl 4,4 ' -diphenylmethane dicarbamic acid, butyl 4,4 ' -diphenylmethane dicarbamic acid, pentyl 4,4 ' -diphenylmethane dicarbamic acid, hexyl 4,4 ' -diphenylmethane dicarbamic acid, heptyl 4,4 ' -diphenylmethane dicarbamic acid, octyl 4,4 ' -diphenylmethane dicarbamic acid, nonyl 4,4 ' -diphenylmethane dicarbamic acid, and decyl 4,4 ' -diphenylmethane dicarbamic acid.
6. The continuous method for synthesizing alicyclic carbamates according to claim 1 wherein said solvent is one or more of liquid paraffin, nitrobenzene, o-nitrotoluene, tetrahydrofuran, diphenyl ether, methyl acetate, dimethyl carbonate, diisooctyl phthalate, dioctyl sebacate, dimethyl phthalate, dibutyl phthalate, N-dimethylacetamide and dimethylsulfoxide.
7. The continuous synthesis method of alicyclic carbamates according to claim 1 wherein said solvent is preferably one or more of methyl acetate, dimethyl carbonate, N-dimethylacetamide, diisooctyl phthalate, dioctyl sebacate, dimethyl phthalate or dibutyl phthalate.
8. The continuous synthesis method of alicyclic urethanes according to claim 1, wherein the temperature of the preheater is preferably 40 to 80 ℃; the temperature of the reactor is preferably 60-100 ℃.
9. The continuous synthesis method of alicyclic urethanes according to claim 1, wherein the reaction pressure is preferably 1 to 3 MPa.
10. The continuous synthesis of alicyclic carbamates according to claim 1 wherein said molar ratio is preferably aromatic carbamate: the solvent is 1: 30-1: 300.
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Cited By (4)
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| CN113024418A (en) * | 2021-03-24 | 2021-06-25 | 河北工业大学 | Method for synthesizing alicyclic carbamate by using isopropanol as hydrogen source |
| CN114644576A (en) * | 2022-04-21 | 2022-06-21 | 中国科学院过程工程研究所 | 1, 3-cyclohexanedimethylene dicarbamate and preparation method and application thereof |
| CN115745840A (en) * | 2022-11-07 | 2023-03-07 | 万华化学集团股份有限公司 | Preparation method and application of methylcyclohexyl diisocyanate |
| WO2023168889A1 (en) * | 2022-03-07 | 2023-09-14 | 中国科学院过程工程研究所 | Preparation method for alicyclic carbamate and use thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024418A (en) * | 2021-03-24 | 2021-06-25 | 河北工业大学 | Method for synthesizing alicyclic carbamate by using isopropanol as hydrogen source |
| CN113024418B (en) * | 2021-03-24 | 2023-01-24 | 河北工业大学 | Method for synthesizing alicyclic carbamate by using isopropanol as hydrogen source |
| WO2023168889A1 (en) * | 2022-03-07 | 2023-09-14 | 中国科学院过程工程研究所 | Preparation method for alicyclic carbamate and use thereof |
| CN114644576A (en) * | 2022-04-21 | 2022-06-21 | 中国科学院过程工程研究所 | 1, 3-cyclohexanedimethylene dicarbamate and preparation method and application thereof |
| CN115745840A (en) * | 2022-11-07 | 2023-03-07 | 万华化学集团股份有限公司 | Preparation method and application of methylcyclohexyl diisocyanate |
| CN115745840B (en) * | 2022-11-07 | 2024-04-09 | 万华化学集团股份有限公司 | Preparation method and application of methylcyclohexyl diisocyanate |
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