CN110563562B - Extraction and water washing method of trimethylolpropane heavy component - Google Patents
Extraction and water washing method of trimethylolpropane heavy component Download PDFInfo
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- CN110563562B CN110563562B CN201910911668.4A CN201910911668A CN110563562B CN 110563562 B CN110563562 B CN 110563562B CN 201910911668 A CN201910911668 A CN 201910911668A CN 110563562 B CN110563562 B CN 110563562B
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- C07—ORGANIC CHEMISTRY
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
The invention belongs to the field of separation and purification of organic compounds, and particularly relates to a trimethylolpropane heavy component extraction and washing method, which comprises the following steps: diluting trimethylolpropane heavy components with water, adding concentrated sulfuric acid, stirring uniformly, heating and hydrolyzing; adding NaOH to neutralize to PH7 after hydrolysis; heating the extraction bottle, and introducing the raw material solution, the organic phase solvent and water into a multi-stage extraction water washing system; collecting an extraction water phase and an oil phase liquid from an extraction system; and (5) carrying out gas chromatograph detection. The extraction and water washing method has simple process and simple operation, and adopts the self-prepared C 8 、C 9 The solvent is added into the raw material solution to carry out multi-stage extraction and water washing at a specified temperature, so that the content of impurities such as trimethylolpropane in the trimethylolpropane heavy component can be effectively reduced, the yield of ditrimethylolpropane in the later period is improved, the recovery and the utilization of the trimethylolpropane heavy component are facilitated, and the effects of energy conservation, emission reduction, environmental protection and saving are achieved.
Description
Technical Field
The invention belongs to the technical field of separation and purification of organic compounds, and particularly relates to an extraction and water washing method of trimethylolpropane heavy components.
Background
Di-trimethylolpropane (Di-TMP, CAS No. 23235-61-2) is a molecule with a planar structure, has 4 relatively active primary hydroxyls, has better performance than trimethylolpropane, can replace polyols such as glycerol, neopentyl glycol, pentaerythritol, trimethylolpropane and the like, is used for producing alkyd resin, polyurethane resin, lubricant, explosive, plasticizer, rosin ester and high-grade aviation lubricating oil, and particularly has unique performance in the aspect of application of surfactant and aviation lubricating oil; ditrimethylolpropane is also a raw material for the production of acrylic monomers/oligomers, synthetic lubricants, specialty resins and chemical intermediates, coating resins, PVC stabilizers and other fine chemicals.
Ditrimethylolpropane is generally extracted as a byproduct in the production process of trimethylolpropane, the still residue for extracting ditrimethylolpropane can be obtained by the steps of reaction, evaporation and dehydration, extraction, solvent recovery, rectification, purification and the like from the beginning of feeding, then ditrimethylolpropane is extracted by rectifying the extracted trimethylolpropane still residue, and the purification is generally realized by adopting the methods of firstly dissolving, activated carbon adsorption and decoloration and then crystallization.
At present, trimethylolpropane heavy component extraction is adopted in ditrimethylolpropane production, a crystallization technology is mostly adopted, ditrimethylolpropane is enriched and purified through recrystallization, impurities in the heavy component such as trimethylolpropane can affect crystallization separation of ditrimethylolpropane, and therefore the yield of ditrimethylolpropane is affected to be less than 98%. Therefore, a technical method is urgently needed to reduce the content of impurities such as trimethylolpropane in the heavy component before crystallization, so as to improve the yield of ditrimethylolpropane in the later period and ensure that the yield is more than 98%.
Disclosure of Invention
The invention aims to provide an extraction and water washing method of trimethylolpropane heavy components, which can effectively reduce the content of impurities such as trimethylolpropane and the like in the trimethylolpropane heavy components.
In order to solve the problems, the technical scheme provided by the invention is a trimethylolpropane heavy component extraction and washing method, which comprises the following steps:
s1, taking the trimethylolpropane heavy component, adding water for dilution, adding concentrated sulfuric acid for stirring, and hydrolyzing at 80-90 ℃ for 2-4 hours;
s2, adding NaOH to neutralize to PH7 after hydrolysis is finished;
s3, heating an extraction bottle, and enabling the raw material solution obtained in the step S2, the organic phase solvent and water to enter a multistage extraction water washing system;
s4, collecting an extraction water phase and an oil phase liquid from the extraction system; the collected water phase and oil phase are dehydrated by a rotary evaporator respectively, 0.5g of the oil phase is added with 5ml of acetic anhydride to be esterified for 1 hour at 150 ℃, and then the detection is carried out by a gas chromatograph.
Furthermore, the proportion of trimethylolpropane recombinant to water in S1 is 1:1, and concentrated sulfuric acid is 3 per mill of the total mass.
Furthermore, the original contents of all components in the trimethylolpropane heavy component in the S1 are 36-42% of trimethylolpropane, 41-44.5% of ditrimethylolpropane, 4-5.1% of trimethylolpropane and 12-19% of impurities.
Further, the temperature of the extraction flask in S3 was 40-70 ℃.
Further, the raw material solution in the S3 is pumped into the extraction water washing system from the feed inlet, the organic solvent enters the extraction bottle from the oil phase inlet, and the water is pumped into the extraction bottle from the water phase inlet.
The multi-stage extraction system is used for one-stage upward extraction from bottom to top, the water phase of the whole system flows into a lower-stage extraction bottle by self flow, and the oil phase is pumped into the upper-stage extraction bottle by a pump step by step.
Further, the organic solvent in S3 is C 8 、C 9 Mixed solvent in the proportion of C 8 ：C 9 1-2: 2-3 of which C 8 Is one of dimethylbenzene, octanol, isooctanol and ethylbenzene, C 9 Is one of pseudocumene and methyl ethyl benzene.
Further, the ratio of the raw material solution, the organic solvent and the water in the S3 is 5:7: 10.
Further, the content detected by the gas chromatograph in S4 is the area percentage content obtained by the normalization method, and the content requirements of each component of the extracted water phase are as follows: greater than or equal to 50.5 percent of ditrimethylolpropane, greater than or equal to 45 percent of trimethylolpropane, less than or equal to 0.7 percent of trimethylolpropane and less than or equal to 3.8 percent of other substances.
The invention has the beneficial effects that: the extraction and water washing method has simple process and simple operation, and adopts C 8 、C 9 The mixed solvent is added into the raw material solution to carry out multi-stage extraction and water washing at a specified temperature, so that the content of impurities such as trimethylolpropane in the trimethylolpropane heavy component can be effectively reduced, the yield of ditrimethylolpropane in the later period is improved, the recovery and the utilization of the trimethylolpropane heavy component are facilitated, and the effects of energy conservation, emission reduction, environmental protection and saving are achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In one embodiment of the invention, the method for extracting and washing the trimethylolpropane heavy component comprises the following steps:
s1, adding water to dilute trimethylolpropane heavy components according to the mass ratio of 1:1, adding 3 per mill of concentrated sulfuric acid in total mass, stirring uniformly, hydrolyzing at 80-90 ℃ for 2-4 hours, and hydrolyzing acetal into useful components of cyclotrimethylol formal CTF and trimethylolpropane, wherein the hydrolysis equation is as follows:
s2, adding NaOH to neutralize to PH7 after hydrolysis is finished;
s3, heating the extraction flask to 40-70 ℃, and mixing the raw material solution obtained in the step S2 and the solution C 8 And C 9 The mixed solvent and water enter a five-stage extraction water washing system, and the raw material solution enters from the topA material inlet is filled, the mixture enters an extraction water washing system, an organic solvent enters an extraction bottle from an oil phase inlet, and water enters the extraction bottle from a water phase inlet; preferably, the five-stage extraction system is used for one-stage upward extraction from bottom to top, the water phase of the whole system flows into a lower-stage extraction bottle by self-flow, and the oil phase is pumped into an upper-stage extraction bottle by a pump step by step;
s4, collecting an extraction water phase and an oil phase liquid from the extraction system; dehydrating the collected water phase liquid and oil phase liquid by using a rotary evaporator respectively, adding 0.5g of acetic anhydride into 5ml of the water phase liquid and the oil phase liquid, esterifying for 1 hour at 150 ℃, and detecting by using a gas chromatograph;
the content of each component of the extracted water phase is required to be as follows: greater than or equal to 50.5 percent of ditrimethylolpropane, greater than or equal to 45 percent of trimethylolpropane, less than or equal to 0.7 percent of trimethylolpropane and less than or equal to 3.8 percent of other substances.
Example 1
1. Taking 2Kg of trihydroxy heavy component, adding water for dilution according to the mass ratio of 1:1, adding concentrated sulfuric acid with the total mass of 3 per mill, stirring uniformly, hydrolyzing for 2-4 hours at 80 ℃, and hydrolyzing acetal into useful components of cyclotrihydroxy formal CTF and trimethylolpropane;
2. adding NaOH to neutralize to PH7 for later use after hydrolysis;
3. opening the rotor of the extraction bottle to stir and heat to 45 ℃;
4. preventing the ditrimethylol crystals in the water phase from blocking the pipeline at low temperature, and starting to pump the neutralized raw material solution and C after the temperature in the extraction flask reaches 45 DEG C 8 And C 9 The mixed solvent and water are pumped into a five-stage extraction water washing system, wherein C 8 Is octanol, C 9 Is pseudocumene, C 8 ：C 9 ＝1:2；
5、C 8 、C 9 Pumping the mixed solvent into an extraction bottle from an oil phase inlet, pumping water into the extraction bottle from a water phase inlet, pumping the raw material solution into an extraction water washing system from a feed inlet, and automatically flowing the water phase of the whole system into a next-level extraction bottle C 8 、C 9 Pumping the mixed solvent into an upper extraction bottle step by using a pump;
6. collecting an extraction water phase and an oil phase liquid;
7. dehydrating the collected water phase by using a rotary evaporator, adding 0.5g of acetic anhydride into 5ml of the water phase, esterifying for 1 hour at the temperature of 150 ℃, and detecting by using a gas chromatograph;
8. the collected oil phase was dehydrated by a rotary evaporator, 0.5g was added to 5ml of acetic anhydride and esterified at 150 ℃ for 1 hour, followed by detection by gas chromatography.
Example 2
1. Taking 2Kg of trihydroxy heavy component, adding water for dilution according to the mass ratio of 1:1, adding concentrated sulfuric acid with the total mass of 3 per mill, stirring uniformly, hydrolyzing for 2-4 hours at 80 ℃, and hydrolyzing acetal into useful components of cyclotrihydroxy formal CTF and trimethylolpropane;
2. adding NaOH to neutralize to PH7 after hydrolysis, and keeping it in reserve;
3. opening the rotor of the extraction bottle to stir and heat to 45 ℃;
4. preventing the ditrimethylol crystals in the water phase from blocking the pipeline at low temperature, and starting to pump the neutralized raw material solution and C after the temperature in the extraction flask reaches 45 DEG C 8 And C 9 The mixed solvent and water are pumped into a five-stage extraction and water washing system, wherein C 8 Is octanol, C 9 Is pseudocumene, C 8 ：C 9 ＝2:3；
5、C 8 、C 9 Pumping the mixed solvent into an extraction bottle from an oil phase inlet, pumping the water phase into the extraction bottle from a water phase inlet, pumping the raw materials into an extraction water washing system from a feed inlet, enabling the water phase of the whole system to flow into a lower-level extraction bottle by self-flow, and pumping the oil phase into an upper-level extraction bottle step by using a pump;
6. collecting an extraction water phase and an oil phase liquid;
7. dehydrating the collected water phase by using a rotary evaporator, adding 0.5g of acetic anhydride into 5ml of the water phase, esterifying for 1 hour at the temperature of 150 ℃, and detecting by using a gas chromatograph;
8. the collected oil phase was dehydrated by a rotary evaporator, 0.5g was added to 5ml of acetic anhydride and esterified at 150 ℃ for 1 hour, followed by detection by gas chromatography.
Example 3
1. Taking 2Kg of trihydroxy heavy component, adding water for dilution according to the mass ratio of 1:1, adding concentrated sulfuric acid with the total mass of 3 per mill, stirring uniformly, hydrolyzing for 2-4 hours at 80 ℃, and hydrolyzing acetal into useful components of cyclotrihydroxy formal CTF and trimethylolpropane;
2. adding NaOH to neutralize to PH7 for later use after hydrolysis;
3. opening rotor stirring of the extraction bottle and heating to 65 ℃;
4. preventing the ditrimethylol crystals in the water phase from blocking the pipeline at low temperature, and starting to pump the neutralized raw material solution and C after the temperature in the extraction flask reaches 65 DEG C 8 And C 9 The mixed solvent and water are pumped into a five-stage extraction water washing system, wherein C 8 Is octanol, C 9 Is pseudocumene, C 8 ：C 9 ＝2:3；
5、C 8 、C 9 Pumping the mixed solvent into an extraction bottle from an oil phase inlet, pumping water into the extraction bottle from a water phase inlet, pumping the raw materials into an extraction water washing system from a feed inlet, enabling the water phase of the whole system to flow into a lower-level extraction bottle by self-flow, and pumping the oil phase into an upper-level extraction bottle by a pump step by step;
6. collecting an extraction water phase and an oil phase liquid;
7. dehydrating the collected water phase by using a rotary evaporator, adding 0.5g of acetic anhydride into 5ml of the water phase, esterifying for 1 hour at the temperature of 150 ℃, and detecting by using a gas chromatograph;
8. the collected oil phase was dehydrated by a rotary evaporator, 0.5g was added to 5ml of acetic anhydride and esterified at 150 ℃ for 1 hour, followed by detection by gas chromatography.
Three sets of example test data are as follows:
the results show that after extraction, the content of impurities such as the trihydroxy ditrimethylol and the like in the water phase is obviously reduced, the content of the trihydroxy ditrimethylol is improved, and the yield of the trihydroxy ditrimethylol in the later period is ensured to be more than or equal to 98 percent.
The above disclosure is only one preferred embodiment of the present invention, and certainly should not be construed as limiting the scope of the invention, which is defined by the claims and their equivalents.
Claims (6)
1. The extraction and water washing method of trimethylolpropane heavy components is characterized by comprising the following steps:
s1, taking the trimethylolpropane heavy component, adding water for dilution, adding concentrated sulfuric acid for stirring, and hydrolyzing at 80-90 ℃;
s2, adding NaOH to neutralize to PH7 after hydrolysis is finished;
s3, heating an extraction bottle, and enabling the raw material solution obtained in the step S2, the organic phase solvent and water to enter a multistage extraction water washing system; the organic solvent is C 8 、C 9 Mixed solvent in the proportion of C 8 ：C 9 1-2: 2-3 of which C 8 Is octanol, C 9 Is pseudocumene;
s4, collecting an extraction water phase and an oil phase liquid from the extraction system; dewatering the collected water phase and oil phase liquid by a rotary evaporator respectively, adding 0.5g of acetic anhydride into 5ml of acetic anhydride, esterifying for 1 hour at 150 ℃, and detecting by a gas chromatograph, wherein the content of each component of the extracted water phase detected by the gas chromatograph is as follows: greater than or equal to 50.5 percent of ditrimethylolpropane, greater than or equal to 45 percent of trimethylolpropane, less than or equal to 0.7 percent of trimethylolpropane and less than or equal to 3.8 percent of impurities.
2. The method for extracting and washing the trimethylolpropane heavy component according to claim 1, wherein the ratio of the trimethylolpropane heavy component to water in S1 is 1:1, and concentrated sulfuric acid is 3 per thousand of the total mass.
3. The method for extracting and washing the trimethylolpropane heavy component according to claim 1, wherein the original content of each component in the trimethylolpropane heavy component in the S1 is 36-42% of trimethylolpropane, 41-44.5% of ditrimethylolpropane, 4-5.1% of trimethylolpropane and 12-19% of impurities.
4. The method for extracting and washing trimethylolpropane heavy components according to claim 1, wherein the temperature of the extraction flask in S3 is 40-70 ℃.
5. The method for extracting and washing trimethylolpropane heavy components according to claim 1, wherein the raw material solution in S3 is pumped from a feed inlet and enters the extraction and washing system, the organic solvent enters the extraction bottle from an oil phase inlet, and the water is pumped into the extraction bottle from a water phase inlet.
6. The method for extracting and washing trimethylolpropane heavy components according to claim 1, wherein the ratio of the raw material solution, the organic solvent and the water in S3 is 5:7: 10.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102143931A (en) * | 2008-08-16 | 2011-08-03 | 朗盛德国有限责任公司 | Method for isolating di-trimethylol propane |
| CN103467252A (en) * | 2013-09-05 | 2013-12-25 | 百川化工(如皋)有限公司 | Method for increasing purity of di-trimethylolpropane |
| CN108675919A (en) * | 2018-06-25 | 2018-10-19 | 南通百川新材料有限公司 | A kind of method that double trimethylolpropane is extracted in trimethylolpropane heavy constituent |
| CN109485554A (en) * | 2018-11-27 | 2019-03-19 | 濮阳市永安化工有限公司 | The method of double trimethylolpropane is isolated from trimethylolpropane heavy constituent |
| CN110156565A (en) * | 2019-07-01 | 2019-08-23 | 南通百川新材料有限公司 | A kind of method of trimethylolpropane extraction washing |
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- 2019-09-25 CN CN201910911668.4A patent/CN110563562B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102143931A (en) * | 2008-08-16 | 2011-08-03 | 朗盛德国有限责任公司 | Method for isolating di-trimethylol propane |
| CN103467252A (en) * | 2013-09-05 | 2013-12-25 | 百川化工(如皋)有限公司 | Method for increasing purity of di-trimethylolpropane |
| CN108675919A (en) * | 2018-06-25 | 2018-10-19 | 南通百川新材料有限公司 | A kind of method that double trimethylolpropane is extracted in trimethylolpropane heavy constituent |
| CN109485554A (en) * | 2018-11-27 | 2019-03-19 | 濮阳市永安化工有限公司 | The method of double trimethylolpropane is isolated from trimethylolpropane heavy constituent |
| CN110156565A (en) * | 2019-07-01 | 2019-08-23 | 南通百川新材料有限公司 | A kind of method of trimethylolpropane extraction washing |
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