KR20150118808A - Preparation method of hydroxypivaldehyde - Google Patents
Preparation method of hydroxypivaldehyde Download PDFInfo
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- KR20150118808A KR20150118808A KR1020140044913A KR20140044913A KR20150118808A KR 20150118808 A KR20150118808 A KR 20150118808A KR 1020140044913 A KR1020140044913 A KR 1020140044913A KR 20140044913 A KR20140044913 A KR 20140044913A KR 20150118808 A KR20150118808 A KR 20150118808A
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- paraformaldehyde
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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- 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
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
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Abstract
Description
The present invention relates to a process for the preparation of hydroxypivalaldehyde using paraformaldehyde aqueous solution.
Hydroxypivalaldehyde (hereinafter HPA) is generally prepared by aldol reaction of isobutylaldehyde and formaldehyde in the presence of a basic catalyst. The HPA is often used as an intermediate of organic compounds such as neopentyl glycol and spiroglycol, and the organic layer and the water layer are separated from each other by using octanol and used immediately in the next step. The organic layer contains unreacted i-BAL and crude HPA, and the water layer contains a salt-containing catalyst. After extraction, the organic layer removes the low boiling point material through distillation and is used immediately in the next step. For example, when the hydroxypivalic aldehyde is prepared and then hydrogenated, neopentyl glycol is produced.
US Patent Nos. 5,144,408 and 5,146,012 disclose a process for the preparation of paraformaldehyde in the presence of a catalyst comprising at least one oxide of an element selected from the group consisting of 1B, 4A, 4B, 5A, 5B, 6B and 8 of the Periodic Table of Elements and a tertiary amine. Discloses a process for producing HPA by reacting aldehyde with isobutylaldehyde. However, when a metal catalyst is used in the above method, various salts with an organic material are formed. In the subsequent hydrogenation reaction, the amount of byproducts increases and the hydrogenation catalyst is poisoned.
In addition, there is a case where an aqueous solution of formaldehyde containing methanol is used in the production of HPA. However, this method requires methanol wastewater treatment process after completion of the reaction due to methanol, and it is difficult to produce high purity HPA.
It is an object of the present invention to provide a process for producing hydroxypivalaldehyde which is excellent in both product selectivity and conversion of reactants by using an aqueous solution of paraformaldehyde at a specific concentration in the presence of a basic catalyst without addition of an oxidizing agent.
The present invention relates to a process for preparing paraformaldehyde, which comprises dissolving paraformaldehyde in an aqueous solution using a base catalyst to prepare a paraformaldehyde aqueous solution at a concentration of 35 to 42% by weight; And
Aldol reaction of isobutyraldehyde and the 35 to 42 wt% paraformaldehyde aqueous solution in the presence of a base catalyst;
≪ RTI ID = 0.0 > a < / RTI > hydroxypivalate.
The base catalyst may be triethylamine.
The step of preparing the paraformaldehyde aqueous solution comprises the step of preparing a paraformaldehyde aqueous solution having a temperature of 40 to 70 DEG C and a pH of 9 to 12 by using 0.1 to 5 wt% of triethylamine as a base catalyst.
The aldol reaction may be carried out at a reaction pressure of 0 to 200 kPa and 50 to 100 ° C for 30 minutes to 120 minutes. The aldol reaction is preferably carried out for 30 minutes to 60 minutes.
The isobutyraldehyde may be used in a molar ratio of 1: 1 to 1.5 relative to the paraformaldehyde aqueous solution.
In the aldol reaction, the base catalyst is preferably used in an amount of 1: 0.1 to 0.5 mol of triethylamine based on the paraformaldehyde aqueous solution.
According to the present invention, the conversion of isobutyraldehyde is 90 to 100%, and the selectivity of hydroxypivalic aldehyde can be 90% or more.
The method of the present invention is excellent in both the conversion of isobutylaldehyde and the selectivity of HPA, the final product, by using paraformaldehyde together with isobutylaldehyde in an aldol reaction for preparing HPA by dissolving paraformaldehyde in a specific concentration of aqueous solution The reaction time is very short and the dissolution of paraformaldehyde is easy, thereby preventing the generation of waste water.
Fig. 1 is a graph showing the i-BAL conversion and HPA selectivity as a result of aldol reaction of a paraformaldehyde aqueous solution of the examples.
FIG. 2 is a graph showing the i-BAL conversion and HPA selectivity as a result of aldol reaction of anhydrous paraformaldehyde of Comparative Example.
FIG. 3 is a graph showing the i-BAL conversion and the HPA selectivity as a result of an aldol reaction test on paraformaldehyde not completely dissolved by adding TEA of the comparative example.
FIG. 4 is a graph showing the i-BAL conversion and HPA selectivity as a result of aldol reaction of an aqueous paraformaldehyde solution containing methanol of the comparative example.
FIG. 5 is a graph showing the i-BAL conversion and HPA selectivity as a result of aldol reaction of a 45% paraformaldehyde aqueous solution of Comparative Example.
Hereinafter, the present invention will be described in detail.
According to a preferred embodiment of the present invention, there is provided a process for preparing paraformaldehyde, which comprises dissolving paraformaldehyde in an aqueous solution using a base catalyst to prepare a paraformaldehyde aqueous solution having a concentration of 35 to 42% by weight; And aldol reaction of isobutyraldehyde and the 35 to 42% by weight aqueous solution of paraformaldehyde in the presence of a base catalyst.
The present invention relates to a process for preparing hydroxypivalaldehyde (HPA) which is an intermediate product of neopentyl glycol (NPG). More particularly, the present invention relates to a process for producing HPA which is environmentally friendly and economical by shortening the reaction time, increasing the selectivity and omitting the wastewater treatment process.
The HPA is produced by an aldol reaction under a triethylamine (TEA) catalyst of isobutylaldehyde (i-BAL) and paraformaldehyde (p-FA). In the present invention, paraformaldehyde is dissolved in a base catalyst and water It is used as an aqueous solution of a specific concentration.
The conventional method of producing HPA uses 35 to 37% aqueous solution of formaldehyde, but often contains methanol. The aqueous solution of 35 to 37% formaldehyde may cause problems in the production of high purity hydroxypivalic aldehyde due to the lowering of the formaldehyde concentration or the polymerization due to the methanol content. When a formaldehyde aqueous solution containing methanol is used as a reaction raw material, the methanol component in crude hydroxypivaldehyde should be removed.
As for the route of methanol, the absolute amount of methanol in crude hydroxypivalaldehyde is distributed to the organic phase in the extraction process, and the relative weight fraction remains in the water phase of the inorganic phase. Methanol remaining in the water layer is circulated with the recovery of the catalyst, and this methanol is added to the methanol introduced into formaldehyde while moving to increase the proportion of components and accumulate methanol to make high purity hydroxypivalate.
However, such a problem can be solved by dissolving paraformaldehyde in an aqueous solution as in the present invention. In addition, the formaldehyde aqueous solution generally requires a wastewater treatment process after the aldol reaction, but according to the present invention, it is possible to reduce the wastewater treatment process by using a paraformaldehyde aqueous solution of a specific concentration. In particular, since the paraformaldehyde aqueous solution can be easily recovered in the present invention, the concentration of the paraformaldehyde aqueous solution can be adjusted to 35 to 42% by weight through recycling of the paraformaldehyde aqueous solution.
Therefore, the process of the present invention replaces the aldol reaction with a conventional 35-37% formaldehyde aqueous solution with paraformaldehyde, using a paraformaldehyde aqueous solution at a concentration of 35-42 wt%, most preferably 37 wt% Hydroxypivalaldehyde, which is an intermediate product of pentyl glycol. Then, the method of the present invention will be described in more detail.
The paraformaldehyde has low solubility in water, but when pH is adjusted, it easily dissolves in a basic atmosphere. Therefore, in the present invention, the pH is adjusted to 9-12 using a base catalyst, whereby a paraformaldehyde solution having a concentration of 35 to 42%, preferably 37% by weight, is prepared and used for aldol reaction.
The base catalyst may be triethylamine, and the base catalyst may be used for both preparation of paraformaldehyde aqueous solution and aldol reaction.
According to a preferred embodiment of the present invention, the step of preparing the aqueous solution of paraformaldehyde is carried out by using 0.1 to 5% of triethylamine as a base catalyst, and heating at a temperature of 40 to 70 ° C and a pH of 9 to 12 To form an aqueous formaldehyde solution.
If the concentration of the paraformaldehyde aqueous solution is less than 35 wt%, the concentration of formaldehyde is excessively low. If the concentration of formaldehyde exceeds 42 wt%, the amount of the triethylamine catalyst used to dissolve is inefficiently increased, The selectivity of HPA is decreased. When the amount of triethylamine used in the preparation of the paraformaldehyde aqueous solution is less than 0.1%, there is a problem that the paraformaldehyde is not completely dissolved. When the amount exceeds 3%, there is no increase in the dissolution efficiency, to be.
Meanwhile, according to the present invention, the paraformaldehyde aqueous solution prepared above is used for the aldol reaction.
According to a preferred embodiment of the present invention, there is provided a process for aldol reaction of isobutyraldehyde and the 35 to 42 wt% paraformaldehyde aqueous solution in the presence of a base catalyst.
In the aldol reaction, the aldol reaction is preferably carried out at a reaction pressure of 0 to 200 kPa and 50 to 100 ° C for 30 to 120 minutes. Further, it is more preferable that the aldol reaction is carried out for 30 minutes to 60 minutes. In the case of the present invention, by using the above-mentioned paraformaldehyde aqueous solution at a specific concentration, it is possible to remarkably shorten the aldol reaction time and produce HPA having excellent selectivity in a short time.
When the aldol reaction proceeds, the isobutyraldehyde may be used in a molar ratio of 1: 1 to 1.5 based on the paraformaldehyde aqueous solution.
In the aldol reaction, the base catalyst is preferably used in an amount of 1: 0.1 to 0.5 mol of triethylamine based on the paraformaldehyde aqueous solution.
In the present invention, the conditions of the reactor used in the aldol reaction are not particularly limited, and all well known reactors can be used. Further, after completion of the aldol reaction, the paraformaldehyde aqueous solution can be recovered through recycling and can be reused in the aldol reaction by dissolving in a 37% by weight aqueous paraformaldehyde solution.
According to the method for producing HPA of the present invention, the conversion of isobutyraldehyde is 90 to 100%, and the selectivity of hydroxypivalate is 90% or more.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.
<Examples>
The experiment was conducted under the conditions of I-BAL: p-FA: TEA = 1 to 1.5: 1: 0.1 to 0.5 (mol).
To dissolve paraformaldehyde in 37% aqueous solution, 0.1% of triethylamine was added to a mixture of 96.6 g of paraformaldehyde and 65.2 g of water and dissolved. At this time, the temperature was set to 60 ° C and the pH was set to 10.
Thereafter, isobutylaldehyde (161.9 g) and paraformaldehyde aqueous solution (162.2 g) were reacted in an aldol reactor in the presence of triethylamine (20.4 g) catalyst. The aldol reaction was carried out at a reaction temperature of 72 ° C, a reaction pressure of 200 kPa, and a reaction time of 30 minutes to 60 minutes.
Gas Chromatography analysis results for the products after the aldol reaction are shown in Table 1. As a result of the aldol reaction of the paraformaldehyde aqueous solution of the examples, a graph of i-BAL conversion and HPA selectivity is shown in Fig.
HPA: Hydroxypivalate
NPG isobutyrate: hydroxypivalic acid isobutyl alcohol ester
HPNE: hydroxypivalic acid neopentyl glycol ester
TEA: triethylamine
Referring to the results of Table 1 and FIG. 1, in the example of the present invention, 90 to 100% reaction was performed based on i-BAL: p-FA = 1: The selectivity and HPA yield (= i-BAL conversion x HPA selectivity) were 84.2%.
≪ Comparative Example 1 &
For reproducibility and comparison of results, aldol reaction was carried out in the same manner as in Example except that paraformaldehyde (Aristech) (63.2 g) was used. As a result of the aldol reaction test for the anhydrous paraformaldehyde, a graph of i-BAL conversion and HPA selectivity is shown in Fig.
2, it was confirmed that the reaction time was very long (6 hours) in the comparative example, the HPA selectivity was also lowered, and the final HPA yield was 46.8%.
≪ Comparative Example 2 &
The aldol reaction was carried out in the same manner as in Example using an aqueous solution of paraformaldehyde not completely dissolved but without addition of TEA. As a result of the aldol reaction of the TEA-free paraformaldehyde, a graph of i-BAL conversion and HPA selectivity is shown in FIG.
3, it was confirmed that the conversion rate of i-BAL was similar but the HPA selectivity (54%) was lower and the final HPA yield was 52.4%.
≪ Comparative Example 3 &
The aldol reaction was carried out in the same manner as in Example using paraformaldehyde aqueous solution containing methanol prepared by the following method.
To dissolve paraformaldehyde in 37% aqueous solution, 0.1% of triethylamine was added to a mixture of 96.6 g of paraformaldehyde and 65.2 g of water and dissolved. Methanol was added to 2% of the weight of the paraformaldehyde aqueous solution.
A graph of i-BAL conversion and HPA selectivity is shown in Fig. 4 as a result of the aldol reaction test for the paraformaldehyde aqueous solution containing methanol.
4, it was confirmed that the conversion rate of i-BAL was similar but the selectivity of HPA was low and the final HPA yield was 82.7%.
≪ Comparative Example 4 &
The aldol reaction was carried out in the same manner as in Example using 45% paraformaldehyde aqueous solution prepared by the following method.
5% triethylamine was added to a mixture of 63.4 g of paraformaldehyde and 70.5 g of water in order to dissolve completely in 45% aqueous paraformaldehyde solution.
A graph of i-BAL conversion and HPA selectivity as a result of the aldol reaction of the 45% paraformaldehyde aqueous solution is shown in Fig.
5, the conversion rate of i-BAL is high but HPA selectivity (52%) due to the increase of the byproduct is decreased. As a result, it was confirmed that the final HPA yield was 48.9%.
Claims (8)
Aldol reaction of isobutyraldehyde and the 35 to 42 wt% paraformaldehyde aqueous solution in the presence of a base catalyst;
≪ / RTI >
And 0.1 to 5% of triethylamine as a base catalyst to prepare a paraformaldehyde aqueous solution having a temperature of 40 to 70 DEG C and a pH of 9 to 12. [
Wherein the aldol reaction is carried out at a reaction pressure of 0 to 200 kPa and at 50 to 100 DEG C for 30 to 120 minutes.
Wherein the aldol reaction is carried out for 30 minutes to 60 minutes.
Wherein the base catalyst is 1: 0.1 to 0.5 mol of triethylamine, based on paraformaldehyde aqueous solution.
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| KR1020140044913A KR101655973B1 (en) | 2014-04-15 | 2014-04-15 | Preparation method of hydroxypivaldehyde |
| PCT/KR2015/003185 WO2015160114A1 (en) | 2014-04-15 | 2015-03-31 | Method for preparing hydroxypivaldehyde |
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| KR1020140044913A KR101655973B1 (en) | 2014-04-15 | 2014-04-15 | Preparation method of hydroxypivaldehyde |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020085613A1 (en) * | 2018-10-22 | 2020-04-30 | 주식회사 엘지화학 | Method for manufacturing dimethylolbutanal and method for manufacturing trimethylolpropane using same |
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| CA3136198A1 (en) * | 2019-05-17 | 2020-11-26 | Sika Technology Ag | Process for producing 2,2-dialkyl-3-acyloxypropanals |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0782192A (en) * | 1993-09-10 | 1995-03-28 | Mitsubishi Gas Chem Co Inc | Production of neopentyl glycol |
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| US5144088A (en) * | 1991-04-26 | 1992-09-01 | Aristech Chemical Corporation | Manufacture of neopentyl glycol (I) |
| JP3812598B2 (en) * | 1994-10-20 | 2006-08-23 | 三菱瓦斯化学株式会社 | Method for producing polyhydric alcohol |
| DE102008031338B4 (en) * | 2008-07-02 | 2012-09-13 | Oxea Gmbh | Process for the preparation of neopentyl glycol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0782192A (en) * | 1993-09-10 | 1995-03-28 | Mitsubishi Gas Chem Co Inc | Production of neopentyl glycol |
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| Microscopy Today, Vol.17, pp.48-49 (2009)* * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020085613A1 (en) * | 2018-10-22 | 2020-04-30 | 주식회사 엘지화학 | Method for manufacturing dimethylolbutanal and method for manufacturing trimethylolpropane using same |
| KR20200045211A (en) * | 2018-10-22 | 2020-05-04 | 주식회사 엘지화학 | Preparing method of dimethylolbutanal and preperation method of trimethylolpropane using the same |
| CN112004791A (en) * | 2018-10-22 | 2020-11-27 | Lg化学株式会社 | Method for preparing dimethylolbutanal and method for preparing trimethylolpropane using the same |
| US11008274B2 (en) | 2018-10-22 | 2021-05-18 | Lg Chem, Ltd. | Method for manufacturing dimethylolbutanal and method for manufacturing trimethylolpropane using same |
| JP2021517158A (en) * | 2018-10-22 | 2021-07-15 | エルジー・ケム・リミテッド | A method for producing dimethylolbutanal and a method for producing trimethylolpropane using the same. |
| CN112004791B (en) * | 2018-10-22 | 2023-01-31 | Lg化学株式会社 | Method for preparing dimethylolbutanal and method for preparing trimethylolpropane using the same |
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