CN116425632A - Process method for producing dioctyl carbonate - Google Patents

Process method for producing dioctyl carbonate Download PDF

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CN116425632A
CN116425632A CN202310433970.XA CN202310433970A CN116425632A CN 116425632 A CN116425632 A CN 116425632A CN 202310433970 A CN202310433970 A CN 202310433970A CN 116425632 A CN116425632 A CN 116425632A
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octanol
carbonate
dioctyl carbonate
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water
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杨颛
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Tongling Makeup Technology Co ltd
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Tongling Pengao Technology Co ltd
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    • 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
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/28—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • 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
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    • Y02P20/584—Recycling of catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a process method for producing dioctyl carbonate, which specifically comprises the following steps: (1) Adding dimethyl carbonate and n-octanol into a reaction kettle, and adding a solid base catalyst to perform transesterification reaction to obtain dioctyl carbonate reaction liquid; (2) Distilling the reaction liquid obtained in the step 1 under reduced pressure, concentrating, desolventizing to obtain recovered octanol serving as a solvent sleeve for the step 1; (3) Washing the concentrated solution obtained in the step 2 with water to obtain a water washing solution, and removing the water washing solution from the step 6; (4) Performing steam distillation on the organic layer obtained after the water washing in the step 3, and further recovering octanol; (5) Rectifying the concentrated solution obtained after the distillation in the step 4 under reduced pressure to obtain a dioctyl carbonate finished product; (6) And (3) distilling and dehydrating the water washing liquid obtained in the step (3) to recover the catalyst, and recycling the catalyst to the step (1). The method can realize continuous use of the catalyst without treatment, and the purity and yield of the prepared product can meet the existing purity requirement, and can realize the large-scale production of dioctyl carbonate.

Description

Process method for producing dioctyl carbonate
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a process method for producing dioctyl carbonate.
Background
Dioctyl carbonate is a novel emollient with very dry skin feel and good spreadability, and performance comparable to volatile silicone oils. In addition, the organic sunscreen agent has good solubility to crystalline organic sunscreen agent, titanium dioxide and zinc oxide, and can obviously improve the SPF value of the product and reduce the greasy feel of the sunscreen agent when used in the sunscreen product. As a vegetable-derived fat and oil, dioctyl carbonate has excellent skin compatibility, has low irritation to skin and mucous membrane, and is very suitable for infant products and high-grade skin care products.
At present, the large-scale production of dioctyl carbonate is not realized in China, and the market of the dioctyl carbonate is mainly monopoly basf. The synthesis route of the dioctyl carbonate is to use dimethyl carbonate and n-octanol as raw materials, and use an alkaline catalyst to synthesize the dioctyl carbonate through transesterification. In the existing process of producing dioctyl carbonate, the catalysts used can be divided into two classes: homogeneous catalysts and heterogeneous catalysts. The homogeneous catalyst is mainly soluble transition metal complex and salts (such as sodium carbonate, potassium carbonate and the like), and has higher activity and selectivity, but the separation of the product and the catalyst is difficult, the catalyst cannot be continuously used, and the concept of green environmental protection is not met. Heterogeneous catalysts include supported catalysts of metals, transition metal complexes, metal salts, semiconducting metal oxides, sulfides, solid acids, solid bases, and insulating oxides, among others. According to the catalytic theory, the homogeneous catalyst can provide more catalytic activity compared with the heterogeneous catalyst, which is a main reason that the catalytic effect is better than that of the heterogeneous catalyst, but the homogeneous catalysis causes difficulty in separating the catalyst from the product, so that the purity of the product is influenced, and the regeneration of the catalyst is more difficult than that of the heterogeneous catalyst.
Chinese patent CN115353455a discloses a method for separating a solid catalyst using a centrifugal method, which avoids a step of washing with water, reduces treatment and discharge of salt-containing wastewater, and the catalyst can be reused many times, has no pollutant discharge, and is environment-friendly. However, as described above, in the actual process, the catalyst particles obtained after the reaction are very fine, similar to colloidal substances, so that on the one hand, centrifugation is difficult, and on the other hand, the filtration rate is slow, and on the other hand, collection and recovery of the solid catalyst after centrifugation are difficult due to the small catalyst amount and the small particle size.
In addition, the products prepared by the prior art contain trace impurities and have odor, so that the products cannot meet the demands of downstream cosmetics. Chinese patent CN110857274B discloses a method for obtaining odorless cosmetic grade dioctyl carbonate by resin adsorption and rectification, but the regeneration process after resin adsorption is not mentioned, and resin regeneration is also a technical problem.
Therefore, there is an urgent need to develop a simple green synthesis and purification process for dioctyl carbonate, which realizes the large-scale production of the product and changes the situation that the raw materials are dependent on import for a long time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a process method for producing dioctyl carbonate, which can realize continuous use of a catalyst without treatment, and the purity and yield of the prepared product can meet the existing purity requirement, and can realize large-scale production of dioctyl carbonate.
The invention is realized by the following technical scheme:
a process for producing dioctyl carbonate, comprising the steps of:
(1) Adding dimethyl carbonate and n-octanol into a reaction kettle, and adding a solid base catalyst to perform transesterification reaction to obtain dioctyl carbonate reaction liquid;
(2) Distilling the reaction liquid obtained in the step (1) under reduced pressure, concentrating, desolventizing to obtain recovered octanol serving as a solvent sleeve for the step (1); the octanol content in the obtained concentrated solution is less than 5%;
(3) Washing the concentrated solution obtained in the step (2) with water to obtain a water washing solution, and removing the water washing solution from the step (6);
(4) Performing steam distillation on the organic layer obtained after the water washing in the step (3), further recovering octanol, and removing trace impurities in the octanol; the octanol content in the concentrated solution after steam distillation is less than 0.5%;
(5) Rectifying the concentrated solution obtained after the distillation in the step (4) under reduced pressure to obtain a dioctyl carbonate finished product;
(6) And (3) dehydrating the water washing liquid obtained in the step (3) by distillation until the water content is less than 0.2%, obtaining the catalyst, and returning to the step (1) for reuse.
The invention further improves the scheme as follows:
the solid base catalyst in the step (1) is hydroxide or carbonate of alkali metal, the mass of the solid base catalyst is 0.5-1% of the mass of dimethyl carbonate, and the molar ratio of n-octanol to dimethyl carbonate is 2.1-5.0:1.
Preferably, the solid base catalyst is sodium or potassium hydroxide or carbonate, and the molar ratio of the n-octanol to the dimethyl carbonate is 2.1-3.0:1.
Further, the temperature of the transesterification reaction in the step (1) is 90-140 ℃ and the time is 3-6 hours.
In the step (1), as the reaction temperature increases, methanol produced by the reaction is distilled out of the reaction vessel with the increase in temperature to obtain methanol. In addition, since the reaction of the dimethyl carbonate existing in a small amount is incomplete, the dimethyl carbonate and methanol are liable to be azeotroped, so that a mixture of dimethyl carbonate and methanol is obtained at the time of distillation. The recovered methanol can be reused as raw material in the production process of dimethyl carbonate.
Further, the temperature of the reduced pressure concentration in the step (2) is 110-150 ℃, and the vacuum degree is minus 0.09-minus 0.1MPa.
The octanol distilled and recovered in this step may contain intermediate methyl octyl carbonate and dioctyl carbonate as products, but the reaction effect of the step 1 is not affected because the product is finally converted into dioctyl carbonate. Preferably, this step controls the octanol content of the concentrate to <5% so that the steam distillation operation of step (4) further reduces the octanol content of the concentrate.
Further, the catalyst is separated from the concentrated solution in the step (3) by water washing, wherein the water is used in an amount of 5-10% by weight of the concentrated solution in the step (2).
Further, the steam distillation temperature in the step (4) is 80-100 ℃; the vacuum degree is-0.08 to-0.1 MPa.
In this step, the distilled water amount of the water vapor is not particularly required, and usually, more water amount brings better distillation deodorizing effect, and more water amount brings more energy consumption. Preferably, the water yield by steam distillation is 34-44% of the weight of the concentrated solution in the step 2; the distilled liquid is layered, the water layer can be treated by an environment-friendly center, and the organic layer is collected for solid waste treatment.
Further, the vacuum degree of the reduced pressure rectification in the step (5) is 80-100Pa, and the temperature is 145-155 ℃; the obtained dioctyl carbonate finished product is cosmetic-grade dioctyl carbonate, and the purity is more than 99.0%.
Further, octanol can be added in the distillation dehydration step in the step (6) for azeotropic dehydration, and when the water content in the dehydration liquid is less than 0.2%, the octanol solution of the catalyst is returned to the step (1) for reuse; the amount of octanol to be added is sufficient to achieve a dehydrating effect, preferably the amount of octanol to be added does not exceed the amount of octanol described in step 1.
In summary, compared with the prior art, the invention has the following advantages:
1. according to the invention, dimethyl carbonate and n-octanol are used as raw materials, a solid base catalyst is utilized to synthesize dioctyl carbonate through transesterification, and crude products after light components are removed are distilled and rectified by steam to obtain cosmetic-grade dioctyl carbonate, so that the reaction catalysis effect is good, the side reaction is less, and the yield is high; the water-soluble catalyst is separated out by washing the concentrated solution after the light components are removed, and the catalyst can be continuously used. The product subjected to steam distillation treatment is odorless, the whole process is environment-friendly and economical, and the blank of domestic industrialization of dioctyl carbonate is filled.
2. After the reaction is finished, the catalyst is not subjected to filtering operation, octanol is recovered by reduced pressure distillation, then concentrated solution is subjected to water washing, a water-soluble catalyst is separated from a reaction system, and azeotropic dehydration is carried out by using octanol, so that the catalyst is regenerated, and the catalyst is recycled; the catalyst utilization rate is high, and the production efficiency is improved.
3. In the reaction process, the methanol generated by the reaction can be distilled out along with the temperature increase along with the increase of the reaction temperature, and the reaction is pushed to the direction of dioctyl carbonate along with the continuous separation of the methanol from the reaction system. And the octanol is recovered by distillation, and the reaction is further carried out towards the direction of dioctyl carbonate due to the existence of the catalyst, so that the conversion rate of the reaction is also improved.
4. The invention removes trace impurities in the reaction liquid by adopting steam distillation operation, and rectifies to obtain the product, which is used as a substitute for resin adsorption operation in the prior art, simplifies operation steps, avoids difficult recovery of resin, and realizes controllability of product quality.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Comparative example 1:
dimethyl carbonate (27 g,299.74mmol,1.0 eq.) and n-octanol (117.1 g,899.22mmol,3.0 eq.) are added into a 1 liter reaction bottle, potassium hydroxide (0.168 g,3.00mmol,0.01 eq.) is added, the temperature is raised to 90 ℃ for reaction for 1 hour, then the temperature is raised to 110 ℃ for continuous reaction for 1 hour, and methanol generated by the reaction is distilled and recovered; continuously heating to 130-140 ℃, continuously distilling and recovering methanol for 1-2 hours, and stopping distilling when no liquid drops flow out. The reaction solution is cooled to 20-30 ℃, filtered by a sand core funnel to obtain fine powder adhesive solid, the filtering speed is gradually slowed down, the reaction solution is difficult to be filtered cleanly finally, and the filtering time is longer, namely about 30-40min. The filtrate was allowed to stand at 15-20deg.C for 24-48 hours, and white solid reappeared in the reaction flask.
Comparative example 2:
the potassium hydroxide in comparative example 1 was replaced with potassium carbonate (3.00 mmol) in the same manner as above, and after 1 to 2 times of application of the catalyst, a fine powdery adhesive solid was obtained as well, and the filtration time was long. The filtrate was allowed to stand at 15-20deg.C for 24-48 hours, and white solid reappeared in the reaction flask.
Thus, as disclosed in the prior art, the difficulty in catalyst recovery is the common feature that alkali metal hydroxides or carbonates suffer from.
Example 1:
(1) Dimethyl carbonate (100 g,1.11mol,1.0 eq.) and n-octanol (303.60 g,2.33mol,2.1 eq.) are added to a 1 liter reaction kettle, potassium carbonate (1.53 g,11.11mmol,0.01 eq.) is added, the temperature is raised to 90 ℃ for reaction for 1 hour, then the temperature is raised to 110 ℃ for reaction for 1 hour, and methanol produced by the reaction is distilled and recovered; then heating to 130-140 ℃ and continuously distilling to recover methanol, wherein the reaction time is 1-3 hours. The recovered methanol was combined and the total recovered methanol was about 57.4g (wherein: dimethyl carbonate to methanol ratio was 1:3.35); the ratio of each component in the obtained reaction liquid is dimethyl carbonate: methanol: dioctyl carbonate: methyl octyl carbonate: impurities octanol=0.63:2.87:58.10:12.73:0.28:25.38
(2) Controlling the temperature of the obtained reaction liquid to be 110-150 ℃, and recovering octanol by reduced pressure distillation (-0.09 to-0.1 MPa) through a water pump; the distilled recovered octanol amounted to about 101.5g, where dimethyl carbonate: octanol: dioctyl carbonate: methanol: methyl octyl carbonate: the ratio of impurities is 2.35:68.75:3.44:14.01:11.43:0.01; 256g of the concentrate is obtained, wherein the components are mainly dioctyl carbonate, the proportion is about 88.59%, the other components are mainly octyl alcohol and methyl octyl carbonate, the proportion is respectively 4.78% and 6.25%, and the rest are other impurities.
(3) Cooling the concentrated solution obtained in the step 2 to 20-60 ℃, adding water for washing twice, layering 15g each time (the weight of the concentrated solution in the step 2 is 5.8%), and removing the water layer in the step 6 for the first time and sleeving the water layer in the next water washing step for the second time; the organic layer is distilled by steam in the step 4 to remove trace impurities.
(4) Adding 110g of water into the organic layer obtained in the step 3, heating to 80-100 ℃, distilling under reduced pressure (-0.01 to-0.03 MPa), continuously increasing the vacuum degree to (-0.09 to-0.1 MPa) to 130-140 ℃ for dehydration when the octanol content in the concentrated solution is 0.36%, layering the obtained distilled liquid, removing the wastewater from the water layer (about 110 g), and carrying out concentrated treatment on the organic layer;
(5) And (3) rectifying the distillation concentrated solution obtained in the step (4) at the temperature of between 145 and 155 ℃ under 80 and 100Pa by an oil pump to obtain 214g of refined dioctyl carbonate, wherein the purity of the dioctyl carbonate is 99.3 percent, and collecting 16g of front cut fraction (wherein, octanol is 12.2 percent, dioctyl carbonate is 69.1 percent and methyl octyl carbonate is 18.7 percent).
(6) Adding 260g of n-octanol into the first water washing water obtained in the step 3, pumping water at-0.05 to-0.06 MPa, heating to 40-90 ℃ for dehydration, layering to obtain 15.2g of water layer, and returning to the next batch of step 3 for second water washing; the organic layer was returned to the system for further water removal to a water content of 0.2% in the system, and the resulting mixed liquor was used in example 2.
Example 2
(1) Adding the mixed solution obtained in the step 6 in the example 1 into a reaction kettle, adding octanol distilled and recovered in the step 2 (total about 101.5 g), adding dimethyl carbonate (100 g,1.11mol,1.0 eq.) to react for 1 hour at the temperature of 90 ℃, then heating to 110 ℃ to continue the reaction for 1 hour, and distilling and recovering methanol generated by the reaction; then heating to 130-140 ℃ and continuously distilling to recover methanol. The recovered methanol was combined and the total recovered methanol was about 71.4g (wherein the ratio of dimethyl carbonate to methanol was 1:5.45); the ratio of each component in the obtained reaction liquid is dimethyl carbonate: methanol: dioctyl carbonate: methyl octyl carbonate: impurities octanol=0.31:2.98:63.36:10.80:0.26:22.27
(2) Controlling the temperature of the obtained reaction liquid to be 110-150 ℃, and recovering octanol by reduced pressure distillation (-0.09 to-0.1 MPa) through a water pump; the distilled recovered octanol totaled about 90.5g, where dimethyl carbonate: octanol: dioctyl carbonate: methanol: methyl octyl carbonate: the ratio of impurities is 1.31:68.54:3.43:15.74:10.97:0.017; 292g of the obtained concentrated solution mainly comprises dioctyl carbonate, the proportion of which is about 90.53%, the other components mainly comprise octyl alcohol and methyl octyl carbonate, the proportion of which is 4.04% and 5.09%, respectively, and the rest is other impurities.
(3) Cooling the concentrated solution obtained in the step 2 to 20-60 ℃, adding water for washing twice, adding about 15g of the water for washing the second time in the step 3 in the example 1 for the first time, adding the recycled water (about 5.4% of the weight of the concentrated solution in the step 2) in the step 6 in the example 1 for the second time, layering, removing the water layer for the first time from the step 6, and sleeving the water layer for the next water washing step; the organic layer is distilled by steam in the step 4 to remove trace impurities.
(4) Adding 100g of water into the organic layer obtained in the step 3, heating to 80-100 ℃, distilling under reduced pressure (-0.01 to-0.03 MPa), continuously increasing the vacuum degree to (-0.09 to-0.1 MPa) to 130-140 ℃ for dehydration when the octanol content in the concentrated solution is 0.50%, layering the obtained distilled solution, removing the wastewater from the water layer (about 110 g), and carrying out concentrated treatment on the organic layer;
(5) And (3) rectifying the distillation concentrated solution obtained in the step (4) at the temperature of between 145 and 155 ℃ under 80 and 100Pa by an oil pump to obtain 250g of refined dioctyl carbonate, wherein the purity of the dioctyl carbonate is 99.5%, 17g of front cut fraction (9.28% of octanol, 74.60% of dioctyl carbonate and 16.11% of methyl octyl carbonate) is obtained and collected.
(6) Adding 260g of n-octanol into the first water washing water obtained in the step 3, pumping water at-0.05 to-0.06 MPa, heating to 40-90 ℃ for dehydration, layering to obtain 15.8g of water layer, and returning to the next batch of step 3 for second water washing; the organic layer was returned to the system for further water removal to a water content of 0.15% in the system, and the resulting mixed liquor was used in example 3.
Examples 3 to 8
The catalyst recovered in step 6 of example 2, the octanol sleeve recovered in step 2 was used in example 3, and the recovered catalyst obtained in example 3 and octanol sleeve were used in the following examples, as described in example 2, to give examples 3-8, with the respective batches being supplemented with octanol, dimethyl carbonate weights and the resulting product qualities and compositions as shown in the following table:
Figure BDA0004191312990000061
as shown in the table above, the catalyst and recovered octanol are used in combination with little effect on the yield of the reaction effect dioctyl carbonate product and the quality of the product.
Example 9
The fractions obtained in the rectification in step 5 of examples 1 to 8 were combined to obtain 200g of a mixed solution (wherein octanol was 12.29%, dioctyl carbonate was 71.72%, isooctyl carbonate was 15.90%, and other impurities were 0.09%), and were rectified by an oil pump at 80 to 100Pa and 145 to 155℃to obtain 115g of a refined dioctyl carbonate product, wherein the purity of dioctyl carbonate was 99.23%.
Example 10:
(1) Dimethyl carbonate (100 g,1.11mol,1.0 eq.) and n-octanol (361.43 g,2.78mol,2.5 eq.) are added to a 1 liter reaction kettle, potassium carbonate (0.77 g,5.55mmol,0.005 eq.) is added, the temperature is raised to 90 ℃ for reaction for 1 hour, then the temperature is raised to 110 ℃ for reaction for 1 hour, and methanol produced by the reaction is distilled and recovered; then heating to 130-140 ℃ and continuously distilling to recover methanol. The recovered methanol was combined and the resulting recovered methanol amounted to about 54.76g (where: dimethyl carbonate to methanol ratio was 1:3.75); the ratio of each component in the obtained reaction liquid is dimethyl carbonate: methanol: dioctyl carbonate: methyl octyl carbonate: impurities octanol=0.12:2.83:51.48:11.28:0.24:30.04
(2) Controlling the temperature of the obtained reaction liquid to be 110-150 ℃, and recovering octanol by water pump reduced pressure distillation (-0.09 to-0.1 MPa); the distilled recovered octanol amounted to about 144.74g, with dimethyl carbonate: octanol: dioctyl carbonate: methanol: methyl octyl carbonate: the ratio of impurities is 0.35:78.00:3.90:10.12:7.62:0.01; 263g of the concentrated solution is obtained, the proportion of the components is mainly dioctyl carbonate, the proportion is about 88.32%, the other components are mainly octanol and methyl octyl carbonate, the proportion is respectively 5.01% and 6.29%, and the rest is other impurities.
(3) Cooling the concentrated solution obtained in the step 2 to 20-60 ℃, adding water for washing twice, layering 26g each time (10% of the weight of the concentrated solution in the step 2), removing a water layer in the step 6 for the first time, and sleeving a water layer in the next water washing step for the second time; the organic layer is distilled by steam in the step 4 to remove trace impurities.
(4) Adding 110g of water into the organic layer obtained in the step 3, heating to 80-100 ℃, distilling under reduced pressure (-0.01 to-0.03 MPa), continuously increasing the vacuum degree to (-0.09 to-0.1 MPa) to 130-140 ℃ for dehydration when the octanol content in the concentrated solution is 0.46%, layering the obtained distilled solution, removing the wastewater from the water layer (about 110 g), and carrying out concentrated treatment on the organic layer;
(5) And (3) rectifying the distillation concentrated solution obtained in the step (4) at the temperature of between 145 and 155 ℃ under 80 and 100Pa by an oil pump to obtain 220g of refined dioctyl carbonate product, wherein the purity of the dioctyl carbonate is 99.3 percent, and 16.5g of front cut fraction (wherein, the octanol is 11.26 percent, the dioctyl carbonate is 69.7 percent and the methyl octyl carbonate is 19.1 percent) is obtained and collected.
Example 11:
(1) Dimethyl carbonate (100 g,1.11mol,1.0 eq.) and n-octanol (433.72 g,3.33mol,3.0 eq.) are added to a 1 liter reaction kettle, potassium carbonate (1.07 g,7.77mmol, 0.0070 eq.) is added, the temperature is raised to 90 ℃ for reaction for 1 hour, then the temperature is raised to 110 ℃ for continuous reaction for 1 hour, and methanol produced by the reaction is distilled and recovered; then heating to 130-140 ℃ and continuously distilling to recover methanol. The recovered methanol was combined and the total recovered methanol was about 50.91g (wherein: dimethyl carbonate to methanol ratio was 1:6.14); the ratio of each component in the obtained reaction liquid is dimethyl carbonate: methanol: dioctyl carbonate: methyl octyl carbonate: impurities octanol=0.18:2.79:45.35:9.94:0.21:41.54
(2) Controlling the temperature of the obtained reaction liquid to be 110-150 ℃, and recovering octanol by reduced pressure distillation (-0.09 to-0.1 MPa) through a water pump; the distilled recovered octanol amounted to about 212.23g, with dimethyl carbonate: octanol: dioctyl carbonate: methanol: methyl octyl carbonate: the ratio of impurities is 0.41:82.14:4.11:7.90:5.44:0.007; 272g of the obtained concentrated solution contains mainly dioctyl carbonate, the proportion of which is about 88.36%, other components mainly octanol and methyl octyl carbonate, the proportion of which is 4.91% and 6.37%, respectively, and the rest of other impurities.
(3) Cooling the concentrated solution obtained in the step 2 to 20-60 ℃, adding water for washing twice, layering 22g each time (8% of the weight of the concentrated solution in the step 2), removing a water layer in the step 6 for the first time, and sleeving a water layer in the next water washing step for the second time; the organic layer is distilled by steam in the step 4 to remove trace impurities.
(4) Adding 120g of water into the organic layer obtained in the step 3, heating to 80-100 ℃, distilling under reduced pressure (-0.01 to-0.03 MPa), continuously increasing the vacuum degree to (-0.09 to-0.1 MPa) to 130-140 ℃ for dehydration when the octanol content in the concentrated solution is 0.47%, layering the obtained distilled solution, removing the wastewater from the water layer (about 120 g), and carrying out concentrated treatment on the organic layer;
(5) The distillation concentrated solution obtained in the step 4 is rectified by an oil pump at the temperature of 80-100Pa and 145-155 ℃ to obtain 227g of refined dioctyl carbonate, wherein the purity of the dioctyl carbonate is 99.34%, 17g of front cut fraction (wherein, the octanol is 11.61%, the dioctyl carbonate is 69.23% and the methyl octyl carbonate is 19.16%) is collected.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (9)

1. A process for producing dioctyl carbonate, comprising the steps of:
(1) Adding dimethyl carbonate and n-octanol into a reaction kettle, and adding a solid base catalyst to perform transesterification reaction to obtain dioctyl carbonate reaction liquid;
(2) Distilling the reaction liquid obtained in the step (1) under reduced pressure, concentrating, desolventizing to obtain recovered octanol serving as a solvent sleeve for the step (1); the octanol content in the obtained concentrated solution is less than 5%;
(3) Washing the concentrated solution obtained in the step (2) with water to obtain a water washing solution, and removing the water washing solution from the step (6);
(4) Performing steam distillation on the organic layer obtained after the water washing in the step (3), further recovering octanol, and removing trace impurities in the octanol; the octanol content in the concentrated solution after steam distillation is less than 0.5%;
(5) Rectifying the concentrated solution obtained after the distillation in the step (4) under reduced pressure to obtain a dioctyl carbonate finished product;
(6) And (3) dehydrating the water washing liquid obtained in the step (3) by distillation until the water content is less than 0.2%, obtaining the catalyst, and returning to the step (1) for reuse.
2. A process for producing dioctyl carbonate according to claim 1, wherein: the solid base catalyst in the step (1) is hydroxide or carbonate of alkali metal, the mass of the solid base catalyst is 0.5-1% of the mass of dimethyl carbonate, and the molar ratio of n-octanol to dimethyl carbonate is 2.1-5.0:1.
3. A process for producing dioctyl carbonate according to claim 1, wherein: the temperature of the transesterification reaction in the step (1) is 90-140 ℃ and the time is 3-6 hours.
4. A process for producing dioctyl carbonate according to claim 2, wherein: the solid base catalyst is hydroxide or carbonate of sodium or potassium, and the molar ratio of n-octanol to dimethyl carbonate is 2.1-3.0:1.
5. A process for producing dioctyl carbonate according to claim 1, wherein: the temperature of the reduced pressure concentration in the step (2) is 110-150 ℃, and the vacuum degree is minus 0.09-minus 0.1MPa.
6. A process for producing dioctyl carbonate according to claim 1, wherein: the water consumption in the step (3) is 5-10% of the weight of the concentrated solution in the step (2).
7. A process for producing dioctyl carbonate according to claim 1, wherein: the steam distillation temperature in the step (4) is 80-100 ℃; the vacuum degree is-0.08 to-0.1 MPa.
8. A process for producing dioctyl carbonate according to claim 1, wherein: the vacuum degree of the reduced pressure rectification in the step (5) is 80-100Pa, and the temperature is 145-155 ℃.
9. A process for producing dioctyl carbonate according to claim 1, wherein: and (3) adding octanol in the distillation dehydration step in the step (6) for azeotropic dehydration, and returning the octanol solution of the catalyst to the step (1) for reuse when the water content in the dehydration liquid is less than 0.2%.
CN202310433970.XA 2023-04-21 2023-04-21 Process method for producing dioctyl carbonate Pending CN116425632A (en)

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