CN109485544B - A kind of method for continuously preparing trimethylolpropane - Google Patents
A kind of method for continuously preparing trimethylolpropane Download PDFInfo
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- CN109485544B CN109485544B CN201710810798.XA CN201710810798A CN109485544B CN 109485544 B CN109485544 B CN 109485544B CN 201710810798 A CN201710810798 A CN 201710810798A CN 109485544 B CN109485544 B CN 109485544B
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 100
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000011541 reaction mixture Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 6
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims 3
- 238000010438 heat treatment Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000013043 chemical agent Substances 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YYKMQUOJKCKTSD-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanal Chemical compound CCC(CO)(CO)C=O YYKMQUOJKCKTSD-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种连续制备三羟甲基丙烷的方法，以甲醛、丁醛的混合物为原料，无水乙醇作溶剂，以氢氧化钠水溶液为化剂，使所述混合物与催化剂在毛细管中流动、混合，并在毛细管内形成反应混合物，该反应混合物通过羟醛缩合和歧化反应在毛细管中生成包含三羟甲基丙烷的产物，其中，使反应混合物温度控制为25～75℃，以及增加毛细管长度和/或体积或减少反应混合物流量使反应停留时间为2～25min。本发明缩短了三羟甲基丙烷的合成反应时间(现有技术为4～6h)，收率由75％左右提高到90％。
A method for continuously preparing trimethylolpropane, using a mixture of formaldehyde and butyraldehyde as a raw material, anhydrous ethanol as a solvent, and an aqueous sodium hydroxide solution as a chemical agent, so that the mixture and a catalyst flow and mix in a capillary tube, and a reaction mixture is formed in the capillary, and the reaction mixture generates a product comprising trimethylolpropane in the capillary by aldol condensation and disproportionation, wherein the temperature of the reaction mixture is controlled to 25-75 ° C, and the length of the capillary and/or are increased. Or volume or reduce the flow rate of the reaction mixture to make the reaction residence time 2-25min. The invention shortens the synthesis reaction time of trimethylolpropane (4-6h in the prior art), and the yield is increased from about 75% to 90%.
Description
Technical Field
The present invention relates to a method for continuously preparing trimethylolpropane, and particularly to a method for continuously preparing trimethylolpropane in a capillary tube.
Background
Trimethylolpropane (TMP) is a polyol containing alpha-methyl neopentyl structure, has unique physicochemical characteristics due to the particularity of the molecular structure, and is widely applied to surfactants, coatings, high-grade lubricating oil, printing ink, high-grade aviation grease, plasticizers and glass fiber reinforced plastics. In the production of paint, the performance of alkyd resin prepared by TMP is superior to that of resin prepared by glycerol, neopentyl glycol, pentaerythritol and the like. With the development of the industries such as automobiles, household electrical appliances, ships, transportation and the like in China, the demand of high-grade coatings is greatly increased.
At present, the yield of trimethylolpropane in China is little, the quality needs to be improved, the gap is large, and most of trimethylolpropane is imported. The synthesis of TMP is usually carried out by using an alkaline solution as a catalyst, and formaldehyde and butyraldehyde are subjected to aldol condensation reaction and disproportionation reaction to generate the TMP.
The first step is as follows: aldol condensation reaction of formaldehyde and butyraldehyde
The second step is that: cannizzaro disproportionation of 2, 2-dimethylolbutyraldehyde and formaldehyde
In the prior art, the method for synthesizing TMP is intermittently carried out in a kettle type reactor, and the TMP is reacted for 4-6 hours in a slow dripping mode, so that the yield is limited by a long production period. Therefore, a new process for efficiently and continuously producing TMP is required.
Disclosure of Invention
In order to overcome the defects of difficult control of reaction temperature, long reaction time, low yield and the like in the kettle type reactor for preparing the TMP, the invention provides the method for continuously preparing the TMP by utilizing the micro-reaction technology, which not only can quickly and efficiently prepare the TMP, but also has simple process operation and convenient process regulation.
The specific method of the invention is as follows:
using absolute ethyl alcohol as a solvent, and mixing formaldehyde and n-butyl aldehyde according to a molar ratio of 3-6: 1 to prepare a raw material, wherein the molar concentration of the formaldehyde is 1.5-12 mol/L, and the molar concentration of the n-butyl aldehyde is 0.5-2 mol/L for later use; preparing a sodium hydroxide aqueous solution with the molar concentration of 0.5-2 mol/L for later use; the mixed starting material of formaldehyde and n-butyraldehyde and an aqueous solution of sodium hydroxide were fed into a capillary having a diameter of 0.8 mm by means of an HPLC pump at such a flow rate that the molar ratio of sodium hydroxide to n-butyraldehyde in the reaction mixture was 1: 1. In a capillary tube, a mixed raw material of formaldehyde and n-butyl aldehyde and a sodium hydroxide aqueous solution are respectively preheated to 25-75 ℃ in respective preheating pipelines, preferably to 45-55 ℃; and then the mixture enters a capillary tube to be mixed and reacted, the temperature of the reaction mixture is controlled within the range of 25-75 ℃, the flow rate enables the residence time of the reaction mixture in the capillary tube to be 2-25 minutes, in a preferred or alternative embodiment, the residence time of the reaction mixture in the capillary tube is 5-10 minutes, so that the trimethylolpropane is continuously prepared, and cold fluid with the temperature of-5 ℃ is adopted in an ice water temperature control area, such as cold brine for heat exchange, so as to terminate the reaction.
Adjusting the pH value of the obtained reaction product to about 7 by using formic acid, distilling under reduced pressure to remove ethanol, water, unreacted formaldehyde, n-butyl aldehyde and the like, stopping distillation when a large amount of white solid is separated out, adding a proper amount of absolute ethanol as a solvent, filtering and desalting, continuously distilling the filtrate under reduced pressure to remove the solvent to obtain a crude product. Dissolving the crude product in appropriate amount of anhydrous ethanol, cooling, recrystallizing to obtain white fluid product, vacuum filtering, and drying to obtain white powder product.
Because the n-butyraldehyde is difficult to dissolve in water, the invention takes the absolute ethyl alcohol as the solvent when preparing the mixed solution of the formaldehyde and the n-butyraldehyde, ensures that the formaldehyde and the n-butyraldehyde are uniformly mixed, and simultaneously the absolute ethyl alcohol does not participate in the reaction,
the reaction mixture produces a trimethylolpropane-containing product in the capillary by aldol condensation and disproportionation reactions.
Compared with the prior art, the method can shorten the reaction process time for synthesizing the trimethylolpropane within 30 minutes from the original 6 hours, improve the yield from 75 percent to 90 percent and realize the continuous preparation of the TMP.
Drawings
FIG. 1 is a process flow diagram for synthesizing trimethylolpropane, wherein a 1-liquid caustic soda liquid storage tank, a 2-formaldehyde and n-butyraldehyde mixed solution liquid storage tank, a 3, 4-advection pump, a 5-water bath temperature control area, a 6-sample collection tank and a 7-ice water heat preservation area are adopted.
Detailed Description
The capillary tube was constructed in the reaction system shown in FIG. 1 and used in the following implementation.
Example 1
The method comprises the steps of taking absolute ethyl alcohol as a solvent, preparing a mixed raw material 1 from a formaldehyde aqueous solution and n-butyl aldehyde, wherein the molar concentration of formaldehyde is 10mol/L, the molar concentration of the n-butyl aldehyde is 2mol/L, preparing a sodium hydroxide aqueous solution 2 with the molar concentration of 2mol/L, conveying two materials into a capillary tube at a flow rate of 0.5ml/min by using an HPLC (high performance liquid chromatography) pump 3, controlling the temperature at 55 ℃ in a water bath temperature control region, mixing the two materials after entering the capillary tube from an inlet respectively, reacting in the capillary tube, keeping the materials for 5 ml/(1 ml/min) ═ 5min, and collecting the product to a sample collection tank at an outlet. Adding formic acid into the collected sample to neutralize the pH value to 7, then carrying out reduced pressure distillation, removing water, unreacted n-butyl aldehyde, formaldehyde and the like, dissolving the obtained solid in absolute ethyl alcohol, carrying out suction filtration, carrying out reduced pressure rotary evaporation on the filtrate to remove the ethyl alcohol, cooling and recrystallizing to obtain a solid product. The filtrate was analyzed by gas chromatography, and the yield of trimethylolpropane was calculated to be 90%.
Example 2
The procedure is as in example 1, with only the molar concentrations of the reactants formaldehyde with n-butyraldehyde and catalyst being varied: preparing a mixed raw material from a formaldehyde aqueous solution and n-butyl aldehyde, wherein the molar concentration of the formaldehyde is 5mol/L, the molar concentration of the n-butyl aldehyde is 1mol/L, a sodium hydroxide aqueous solution with the molar concentration of 1mol/L is used as a catalyst, the reaction temperature is 55 ℃, and the material retention time is 5 minutes. The yield of trimethylolpropane obtained was 76%.
Example 3
The process is the same as example 1, only the mixture ratio and molar concentration of the reactants formaldehyde and n-butyraldehyde are changed: the formaldehyde aqueous solution and n-butyl aldehyde are prepared into a mixed raw material, wherein the molar concentration of formaldehyde is 3mol/L, the molar concentration of n-butyl aldehyde is 1mol/L, a sodium hydroxide aqueous solution with the molar concentration of 1mol/L is used as a catalyst, and the material retention time is 5 minutes. The yield of trimethylolpropane obtained was 53%.
Example 4
The procedure is as in example 1, with only the residence times of the reactants formaldehyde and n-butyraldehyde being varied: the formaldehyde aqueous solution and n-butyl aldehyde are prepared into a mixed raw material, wherein the molar concentration of formaldehyde is 3mol/L, the molar concentration of n-butyl aldehyde is 1mol/L, a sodium hydroxide aqueous solution with the molar concentration of 1mol/L is used as a catalyst, the reaction temperature is 55 ℃, and the material retention time is 2.5 minutes. The yield of trimethylolpropane obtained was 46%.
Example 5
The procedure is as in example 1, with only the temperatures of the reactants formaldehyde and n-butyraldehyde being varied: preparing a mixed raw material from a formaldehyde aqueous solution and n-butyl aldehyde, wherein the molar concentration of the formaldehyde is 3mol/L, the molar concentration of the n-butyl aldehyde is 1mol/L, a sodium hydroxide aqueous solution with the molar concentration of 1mol/L is used as a catalyst, the reaction temperature is 45 ℃, and the material retention time is 5 minutes. The yield of trimethylolpropane obtained was 45%.
Claims (10)
1. A method for continuously preparing trimethylolpropane, the method comprising:
using absolute ethyl alcohol as a solvent, and mixing formaldehyde and n-butyl aldehyde according to a molar ratio of (3-6) to 1 to prepare a mixed raw material; sodium hydroxide aqueous solution is used as a catalyst;
flowing and mixing the mixed feedstock and the catalyst in a capillary to form a reaction mixture;
heating the reaction mixture flowing in the capillary tube to 25-75 ℃, and carrying out aldol condensation and disproportionation reaction on the reaction mixture at the temperature to generate a trimethylolpropane-containing product;
wherein the residence time of the reaction mixture in the capillary is 2-25 minutes;
the molar concentration of sodium hydroxide in the catalyst is 0.5-2 mol/L.
2. The method according to claim 1, characterized in that anhydrous ethanol is used as a solvent, and formaldehyde and n-butyl aldehyde are mixed according to a molar ratio of 5:1 to prepare a mixed raw material;
heating the reaction mixture flowing in the capillary to 55 deg.C, and subjecting the reaction mixture to aldol condensation and disproportionation reaction at the temperature to obtain trimethylolpropane-containing product;
wherein the residence time of the reaction mixture in the capillary is 5 minutes.
3. The method according to claim 1, wherein the molar concentration of formaldehyde in the mixed raw material is 1.5-12 mol/L; the molar concentration of the n-butyraldehyde is 0.5-2 mol/L.
4. The method according to claim 3, wherein the molar concentration of formaldehyde in the mixed raw materials is 10 mol/L; the molar concentration of n-butyraldehyde was 2 mol/L.
5. The method of claim 1, wherein the molar concentration of sodium hydroxide in the catalyst is 2 mol/L.
6. The method according to any one of claims 1 to 5, wherein the mixed raw material and the catalyst flow through the capillary at a volume flow rate such that the molar ratio of sodium hydroxide to n-butyraldehyde in the reaction mixture is 0.5 to 2: 1.
7. The method of claim 1, wherein the step of formulating the blended feedstock comprises: mixing formaldehyde and n-butyraldehyde in a preposed capillary, preheating to 25-75 ℃, and introducing into a reaction capillary to contact and react with a catalyst.
8. The method of claim 7, wherein the step of formulating the blended feedstock comprises: mixing formaldehyde and n-butyraldehyde in a preposed capillary, preheating to 55 ℃, and then introducing into a reaction capillary to contact and react with a catalyst.
9. The method according to claim 1, wherein the mixed raw material of formaldehyde and n-butyraldehyde is preheated to 25-75 ℃ before being mixed with the aqueous sodium hydroxide solution, and then the aqueous sodium hydroxide solution is introduced into a reaction capillary tube to contact and react with the raw material.
10. The method according to claim 9, wherein the mixed raw material of formaldehyde and n-butyraldehyde is preheated to 55 ℃ before being mixed with the aqueous sodium hydroxide solution, and then introduced into a reaction capillary to be contacted with the raw material for reaction.
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|---|---|---|---|---|
| CN1428323A (en) * | 2001-12-27 | 2003-07-09 | 拜尔公司 | Process for preparing trialkyl methylpropane |
| CN1263717C (en) * | 2000-08-23 | 2006-07-12 | 拜尔公司 | TMP/steam pressure filtration |
| CN102795964A (en) * | 2012-09-12 | 2012-11-28 | 江西高信有机化工有限公司 | 20000-ton-annual-yield production technique of trimethylolpropane by calcium method |
| CN105431402A (en) * | 2013-08-06 | 2016-03-23 | 欧季亚毕夏普有限责任公司 | Improved manufacture of methylolalkanes |
-
2017
- 2017-09-11 CN CN201710810798.XA patent/CN109485544B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263717C (en) * | 2000-08-23 | 2006-07-12 | 拜尔公司 | TMP/steam pressure filtration |
| CN1428323A (en) * | 2001-12-27 | 2003-07-09 | 拜尔公司 | Process for preparing trialkyl methylpropane |
| CN102795964A (en) * | 2012-09-12 | 2012-11-28 | 江西高信有机化工有限公司 | 20000-ton-annual-yield production technique of trimethylolpropane by calcium method |
| CN105431402A (en) * | 2013-08-06 | 2016-03-23 | 欧季亚毕夏普有限责任公司 | Improved manufacture of methylolalkanes |
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