CN116444372A - Process method for producing diethyl hexyl carbonate - Google Patents
Process method for producing diethyl hexyl carbonate Download PDFInfo
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- CN116444372A CN116444372A CN202310433978.6A CN202310433978A CN116444372A CN 116444372 A CN116444372 A CN 116444372A CN 202310433978 A CN202310433978 A CN 202310433978A CN 116444372 A CN116444372 A CN 116444372A
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- carbonate
- ethylhexanol
- diethyl hexyl
- reaction
- hexyl carbonate
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- PXTQQOLKZBLYDY-UHFFFAOYSA-N bis(2-ethylhexyl) carbonate Chemical compound CCCCC(CC)COC(=O)OCC(CC)CCCC PXTQQOLKZBLYDY-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims abstract description 116
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 14
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000002585 base Substances 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 111
- 239000000243 solution Substances 0.000 description 24
- MKSDSFWGKQOBHN-UHFFFAOYSA-N methyl octyl carbonate Chemical compound CCCCCCCCOC(=O)OC MKSDSFWGKQOBHN-UHFFFAOYSA-N 0.000 description 14
- 239000012535 impurity Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000003921 oil Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- YEWYZOPTNCKBAW-UHFFFAOYSA-N CC(C)CCCCCOC(O)=O Chemical compound CC(C)CCCCCOC(O)=O YEWYZOPTNCKBAW-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GRASKCGOTISKAM-UHFFFAOYSA-N bis(6-methylheptyl) carbonate Chemical compound CC(C)CCCCCOC(=O)OCCCCCC(C)C GRASKCGOTISKAM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- -1 skin conditioner Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process method of diethyl hexyl carbonate, which specifically comprises the following steps: (1) Adding dimethyl carbonate and 2-ethylhexanol into a reaction kettle, and adding a solid base catalyst to perform transesterification reaction to obtain diethyl hexyl carbonate reaction liquid; (2) The reaction liquid obtained in the step 1 is subjected to reduced pressure distillation, concentration and desolventizing to obtain recovered 2-ethylhexanol which is used 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 5; (4) Rectifying the concentrated solution obtained after the distillation in the step 4 under reduced pressure to obtain a finished product of diethyl hexyl carbonate; (5) 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 large-scale production of diethyl hexyl carbonate.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a process method for producing diethyl hexyl carbonate.
Background
Diethyl hexyl carbonate, also known as diisooctyl carbonate (DEHC), is a colorless transparent oil used in cosmetics as a emollient, skin conditioner, dispersant. The diethyl hexyl carbonate has extremely strong polar ester group, good lubricity, wear resistance, self-cleaning property and corrosion resistance, higher thermal oxidation stability and lower pour point, has good solubility with hydrocarbon oil, can be biodegraded, and is also a good environment-friendly lubricating oil base material.
The existing method for synthesizing DEHC mainly comprises a phosgene method, an oxidative carbonylation method, an ester exchange method and the like. The transesterification method is a clean production process, and is synthesized by transesterification of dimethyl carbonate (DMC) and 2-Ethylhexanol (EHOH), and methanol as a byproduct can be used as a raw material for synthesizing the dimethyl carbonate at the same time, so that the dimethyl carbonate can be recycled. The catalyst for synthesizing DEHC by two-step transesterification of DMC and EHOH has few reports, mainly comprises solid alkali, titanate, organic tin/mesoporous carbon and the like, but has the defects of complex preparation and recycling, low catalytic activity and the like, so that the development of a clean and efficient process is very necessary.
At present, the product is mainly produced by the win of Germany, and the domestic productivity is insufficient, so that the development of a simple green synthesis and purification process of diethyl hexyl carbonate is urgently needed at present, the large-scale production of the product is realized, and the situation that the raw materials are dependent on import for a long time is changed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a process method for producing diethyl hexyl 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 diethyl hexyl carbonate.
The invention is realized by the following technical scheme:
a process for producing diethyl hexyl carbonate, comprising the steps of:
(1) Adding dimethyl carbonate and 2-ethylhexanol into a reaction kettle, and adding a solid base catalyst to perform transesterification reaction to obtain diethyl hexyl carbonate reaction liquid;
(2) Distilling the reaction liquid obtained in the step (1) under reduced pressure, concentrating, desolventizing to obtain recovered 2-ethylhexanol serving as a solvent sleeve for the step (1); the content of 2-ethylhexanol 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 (5);
(4) Rectifying the concentrated solution obtained after the distillation in the step (4) under reduced pressure to obtain a finished product of diethyl hexyl carbonate;
(5) And (3) dehydrating the water washing liquid obtained in the step (3) by distillation until the water content is less than 0.1%, 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 the 2-ethylhexanol to the 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 2-ethylhexanol 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 the methanol are liable to be azeotroped, so that a mixture of the dimethyl carbonate and the methanol is obtained at the time of distillation, and the mixture can be returned again to prepare the 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 2-ethylhexanol distilled and recovered in this step may contain methyl octyl carbonate as an intermediate and diethyl hexyl carbonate as a product, and both of them may be converted into products, so that the reaction effect of step 1 is not affected.
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 vacuum degree of the reduced pressure rectification in the step (4) is 80-100Pa, and the temperature is 145-155 ℃; the obtained finished product of the diethyl hexyl carbonate is cosmetic-grade diethyl hexyl carbonate, and the purity is more than 99.0 percent.
Further, adding 2-ethylhexanol in the distillation dehydration step in the step (5) for azeotropic dehydration, and returning the 2-ethylhexanol solution of the catalyst to the step (1) for reuse when the water content in the dehydration liquid is less than 0.1%; the amount of 2-ethylhexanol is sufficient to achieve a dehydration effect, and preferably the amount of 2-ethylhexanol added is not more than the amount of 2-ethylhexanol in step 1.
In summary, compared with the prior art, the invention has the following advantages:
1. according to the invention, dimethyl carbonate and 2-ethylhexanol are used as raw materials, diethyl hexyl carbonate is synthesized by utilizing a solid base catalyst through transesterification, and crude products after light components are removed are distilled and rectified by steam to obtain cosmetic-grade diethyl hexyl 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 industrialization of the diethyl hexyl carbonate in China is filled.
2. After the reaction is finished, the catalyst is not subjected to filtering operation, but is subjected to reduced pressure distillation to recover the 2-ethylhexanol, then the concentrated solution is subjected to water washing, the water-soluble catalyst is separated from a reaction system, and azeotropic dehydration is carried out by using the 2-ethylhexanol, so that the catalyst is regenerated, and 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 rise along with the rise of the reaction temperature, and the reaction is further pushed to the direction of the diethyl hexyl carbonate along with the continuous separation of the methanol from the reaction system. And the 2-ethylhexanol is distilled and recovered, and the reaction is further carried out towards the direction of the diethyl hexyl carbonate due to the existence of the catalyst, so that the conversion rate of the reaction is also improved.
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 2-ethylhexanol (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 2-ethylhexanol (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 to the reaction kettle, the temperature is raised to 90 ℃ for reaction for 1 hour, 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, wherein the reaction time is 1-3 hours. The recovered methanol was combined and the total recovered methanol was about 55.4g (wherein: dimethyl carbonate to methanol ratio was 1:3.35); the ratio of each component in the obtained reaction liquid is dimethyl carbonate: methanol: diethyl hexyl carbonate: methyl octyl carbonate: impurity 2-ethylhexanol=0.64:2.84:57.29:13.22:0.29:25.71;
(2) The temperature of the obtained reaction liquid is controlled to be 110-150 ℃, and 2-ethylhexanol is recovered by reduced pressure distillation (-0.09 to-0.1 MPa) of a water pump; the distilled recovery of 2-ethylhexanol amounted to about 94.33g, with dimethyl carbonate: 2-ethylhexanol: diethyl hexyl carbonate: methanol: methyl octyl carbonate: the ratio of impurities is 2.38:68.57:3.43:13.85:11.75:0.016; the obtained concentrated solution has a weight of 255g, and contains dioctyl carbonate as main component, 2-ethylhexanol and isooctyl carbonate as main component in a proportion of 88.25%, and other impurities as the rest in a proportion of 4.83% and 6.52%, respectively.
(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 5.9%), and removing the water layer in the step 5 for the first time and sleeving the water layer in the next water washing step for the second time; the organic layer goes to step 4 for rectification.
(4) And (3) rectifying the distillation concentrated solution obtained in the step (4) at 80-100Pa and 145-155 ℃ by using an oil pump to obtain 205g of refined diethyl hexyl carbonate, wherein the purity of the diethyl hexyl carbonate is 99.0%, and 39g of front cut fraction (wherein, 2-ethylhexanol is 30.89%, diethyl hexyl carbonate is 28.74% and methyl octyl carbonate is 40.37%) is obtained and collected.
(5) Adding 260g of 2-ethylhexanol 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 until the water content in the system was <0.1% 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 2-ethylhexanol (total about 101.5 g) distilled and recovered in the step 2, 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 simultaneously 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 71.6g (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: diethyl hexyl carbonate: methyl octyl carbonate: mass 2-ethylhexanol=0.31:2.98:63.40:10.78:0.26:22.27
(2) The temperature of the obtained reaction liquid is controlled to be 110-150 ℃, and 2-ethylhexanol is recovered by reduced pressure distillation (-0.09 to-0.1 MPa) of a water pump; the distilled recovery of 2-ethylhexanol amounted to about 90.7g, with dimethyl carbonate: 2-ethylhexanol: diethyl hexyl carbonate: methanol: methyl octyl carbonate: the ratio of impurities is 1.30:68.57:3.43:15.74:10.95:0.017; 293g of the obtained concentrated solution mainly comprises dioctyl carbonate, the proportion of which is about 90.54 percent, the other components mainly comprise 2-ethylhexanol and methyl octyl carbonate, the proportion of which is 4.04 percent and 5.08 percent 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 5.1 percent 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 5, and sleeving the water layer for the next water washing step; the organic layer goes to step 4 for rectification.
(4) The distillation concentrate obtained in the step 4 is rectified by an oil pump at the temperature of 80-100Pa and 145-155 ℃ to obtain 241g of refined diethyl carbonate, wherein the purity of the diethyl carbonate is 99.2%, and 39g of front cut fraction (wherein, 2-ethylhexanol 29.83%, diethyl carbonate 33.95% and methyl octyl carbonate 36.21%) is obtained and collected.
(5) Adding 260g of n-2-ethylhexanol into the first water washing water obtained in the step 3, pumping the water to the pressure of-0.05 to-0.06 MPa, heating the water to the temperature of 40 to 90 ℃ for dehydration, layering the water to obtain 15.8g of a water layer, and returning the water to the next batch of the step 3 for second water washing; the organic layer was returned to the system for further water removal until the water content in the system was <0.1% and the resulting mixed liquor was used in example 3.
Examples 3 to 8
The catalyst recovered in step 6 of example 2, the 2-ethylhexanol jacket recovered in step 2 was used in example 3, and the recovered catalyst obtained in example 3 and the 2-ethylhexanol jacket were used in the following examples, giving examples 3 to 8, the respective batches being supplemented with 2-ethylhexanol, dimethyl carbonate by weight and the resulting product quality and composition as shown in the following table:
as shown in the table above, the catalyst and recovered 2-ethylhexanol sleeve had little effect on the yield of the reaction-effective diethylhexyl carbonate product and on the quality of the product.
Example 9:
(1) Dimethyl carbonate (100 g,1.11mol,1.0 eq.) and 2-ethylhexanol (361.43 g,2.78mol,2.5 eq.) are added into 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 continuous reaction for 1 hour, and methanol generated 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 55.52g (wherein: dimethyl carbonate to methanol ratio was 1:3.76); the ratio of each component in the obtained reaction liquid is dimethyl carbonate: methanol: diethyl hexyl carbonate: methyl octyl carbonate: impurity 2-ethylhexanol=0.08:2.91:53.64:9.94:0.25:33.17
(2) The obtained reaction liquid is distilled under reduced pressure (-0.09 to-0.1 MPa) by a water pump at the temperature of 110-150 ℃ to recover 2-ethylhexanol; the distilled recovery of 2-ethylhexanol amounted to about 141.05g, with dimethyl carbonate: 2-ethylhexanol: diethyl hexyl carbonate: methanol: methyl octyl carbonate: the ratio of impurities is 0.24:78.58:3.93:10.35:6.89:0.01; 266g of the concentrate obtained, the above ingredients being mainly dioctyl carbonate in a proportion of about 89.29%, the other ingredients being mainly 2-ethylhexanol and isooctyl carbonate in a proportion of 4.87% and 5.48%, respectively, the remainder being 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 goes to step 4 for rectification.
(4) The distillation concentrate obtained in the step 4 is rectified by an oil pump at 80-100Pa and 145-155 ℃ to obtain 216g of refined diethyl hexyl carbonate, wherein the purity of the diethyl hexyl carbonate is 99.11%, and 38.35g of front cut fraction (wherein, 2-ethylhexanol 32.97%, diethyl hexyl carbonate 30.95% and methyl octyl carbonate 36.09%) is obtained and collected.
Example 10:
(1) Dimethyl carbonate (100 g,1.11mol,1.0 eq.) and n-2-ethylhexanol (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 51.42g (wherein: dimethyl carbonate to methanol ratio was 1:6.14); the ratio of each component in the obtained reaction liquid is dimethyl carbonate: methanol: diethyl hexyl carbonate: methyl octyl carbonate: impurity 2-ethylhexanol=0.16:2.83:46.61:9.15:0.21:41.03;
(2) The temperature of the obtained reaction liquid is controlled to be 110-150 ℃, and 2-ethylhexanol is recovered by reduced pressure distillation (-0.09 to-0.1 MPa) of a water pump; the distilled recovery of 2-ethylhexanol amounted to about 210g, with dimethyl carbonate: 2-ethylhexanol: diethyl hexyl carbonate: methanol: methyl octyl carbonate: the ratio of impurities is 0.38:82.45:4.12:7.97:5.06:0.007; 274g of the concentrate obtained, the above components mainly consist of dioctyl carbonate, the proportion of which is about 89.00%, the other components mainly consist of 2-ethylhexanol and isooctyl carbonate, the proportions of which are respectively 4.83% and 5.82%, 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 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 goes to step 4 for rectification.
(4) The distillation concentrated solution obtained in the step 4 is rectified by an oil pump at 80-100Pa and 145-155 ℃ to obtain 222g of refined diethyl hexyl carbonate, wherein the purity of the diethyl hexyl carbonate is 99.10%, and 40g of front cut fraction (wherein, 2-ethylhexanol 32.07%, diethyl hexyl carbonate 30.30% and methyl octyl carbonate 37.63%) is obtained and 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 (8)
1. A process for producing diethyl hexyl carbonate, comprising the steps of:
(1) Adding dimethyl carbonate and n-2-ethylhexanol into a reaction kettle, and adding a solid base catalyst to perform transesterification reaction to obtain diethyl hexyl carbonate reaction liquid;
(2) Distilling the reaction liquid obtained in the step (1) under reduced pressure, concentrating, desolventizing to obtain recovered 2-ethylhexanol serving as a solvent sleeve for the step (1); the content of 2-ethylhexanol 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 (5);
(4) Rectifying the water washing liquid obtained in the step (3) under reduced pressure to obtain a finished product of diethyl hexyl carbonate;
(5) And (3) dehydrating the water washing liquid obtained in the step (3) by distillation until the water content is less than 0.1%, obtaining the catalyst, and returning to the step (1) for reuse.
2. A process for producing diethyl hexyl carbonate according to claim 1, characterized in that: 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 the 2-ethylhexanol to the dimethyl carbonate is 2.1-5.0:1.
3. A process for producing diethyl hexyl carbonate according to claim 1, characterized in that: 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 diethyl hexyl carbonate according to claim 2, characterized in that: the solid base catalyst is hydroxide or carbonate of sodium or potassium, and the molar ratio of the n-2-ethylhexanol to the dimethyl carbonate is 2.1-3.0:1.
5. A process for producing diethyl hexyl carbonate according to claim 1, characterized in that: 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 diethyl hexyl carbonate according to claim 1, characterized in that: 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 diethyl hexyl carbonate according to claim 1, characterized in that: the vacuum degree of the reduced pressure rectification in the step (4) is 80-100Pa, and the temperature is 145-155 ℃.
8. A process for producing diethyl hexyl carbonate according to claim 1, characterized in that: and (3) adding 2-ethylhexanol in the distillation dehydration step in the step (6) for azeotropic dehydration, and returning the 2-ethylhexanol solution of the catalyst to the step (1) for reuse when the water content in the dehydration liquid is less than 0.1%.
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