CN101993351A - Process for producing neopentyl glycol - Google Patents
Process for producing neopentyl glycol Download PDFInfo
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- CN101993351A CN101993351A CN2010105311901A CN201010531190A CN101993351A CN 101993351 A CN101993351 A CN 101993351A CN 2010105311901 A CN2010105311901 A CN 2010105311901A CN 201010531190 A CN201010531190 A CN 201010531190A CN 101993351 A CN101993351 A CN 101993351A
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- neopentyl glycol
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Abstract
The invention provides a process for producing neopentyl glycol, which comprises the following steps of: (1) hydrogenating hydroxypivalaldehyde in the presence of an organic solvent under the catalysis of an active nickel catalyst at 60 DEG C-80 DEG C under 1-5MPa; saponifying the hydrogenated product with an inorganic base to obtain a coarse neopentyl glycol product; and (2) refining the coarse neopentyl glycol product obtained in the step (1) to obtain high-purity neopentyl glycol. The process for producing neopentyl glycol has the advantages of few reaction byproducts, high product quality and higher yield.
Description
Technical field
The present invention relates to a kind of preparation method of alcohol, be specifically related to a kind of preparation method of neopentyl glycol.
Background technology
Neopentyl glycol (NPG) is mainly used in and produces unsaturated polyester, polyester powder coating, oil-free alkyd resin, polyurethane foam plastic, is elastomeric softening agent, synthetic softening agent, tensio-active agent, insulating material, printing-ink, stopper, synthetic aircraft oil oil dope etc.In addition, also use to some extent in pharmaceutical industries.Simultaneously, neopentyl glycol or excellent solvent, the selection that can be used for aromatic hydrocarbons and cycloalkyl hydrocarbon polymer separates.
Usually,,, be generally and carry out hydrogenation on the nickel catalyzator, and produce NPG. then at metal catalyst by the condensation of formaldehyde and isobutyric aldehyde.
US3808280 has disclosed the neopentyl glycol method of producing by the aldol reaction of tertiary amine catalyst, exist such problem, that is: the organic acid salify that cannizzaro reaction produced of aldehyde in tertiary amine catalyst and the condensation course, in high temperature hydrogenation process subsequently, make and hydroxy pivalin aldehyde self condensation therefore need to reduce hydrogenation temperature;
Resulting thick neopentyl glycol comprises usually after step of hydrogenation: as the neopentyl glycol and the neopentyl glycol monohydroxy pivalate of by product, because their boiling point is similar to neopentyl glycol, therefore be difficult to from neopentyl glycol, isolate by simple distillation.
Attempted the purify method of thick neopentyl glycol of many kinds already, these methods comprise: solvent extration, vacuum distillation method and crystallization process.US2895996 has disclosed a kind of method of purification of thick neopentyl glycol, and this method comprises: saponification, and distillation subsequently; The characteristic that this method has utilized neopentyl glycol to be easy to distil.Then, owing to need keep low temperature at the top of distillation device, this method is not suitable for industrialization.
In addition, US4935555 has proposed by use the thin film distillation device under vacuum thick neopentyl glycol to be carried out the distillatory method.Yet this method needs expensive equipment, and the yield of neopentyl glycol is lower.
Summary of the invention
The objective of the invention is to: the economic and preparation method capable of being industrialized that the neopentyl glycol of a kind of high purity, high yield is provided.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of neopentyl glycol is provided, and this method comprises the steps:
1) use active nickel catalyst under 60 ℃～80 ℃ temperature and the pressure of 1-5MPa, in the presence of organic solvent, (HPA) carries out hydrogenation to hydroxy pivalin aldehyde, and hydrogenated products re-uses mineral alkali and carries out saponification, obtains the thick product of neopentyl glycol;
2) the thick product of neopentyl glycol that step 1) is obtained is made with extra care, and obtains highly purified neopentyl glycol and refined raffinate.
Above-mentioned steps 1) product after the hydrogenation still has part ester impurity to bring in the product as directly separating, and influences the quality of the finished product, must add alkali soap and eliminate these impurity; Step 2) owing to the existence of organic salt, rectifying also can cause the decomposition of product NPG, must carry out short-path distillation, reduces the material heated time.
The described organic solvent of step 1) can be selected from Fatty Alcohol(C12-C14 and C12-C18) or ether or its mixture; The mixture of one or more in particular methanol, ethanol, propyl alcohol, butanols, ether or the methyl tertiary butyl ether.
The described active nickel catalyst of step 1) preferred various commercially available, through molybdenum, iron and these three kinds of metal-modified active nickel catalysts of chromium, for example the trade mark is the active nickel catalyst of SC3100.
Preferably condensation obtains the described hydroxy pivalin aldehyde of step 1) under tertiary amine catalyst catalysis by formaldehyde and isobutyric aldehyde.After the condensation reaction, do not adopt any further separating measure, reaction mixture is directly used in hydrogenation.
The preferred sodium hydroxide of the described mineral alkali of step 1).
Step 2) described refining preferred use ultra-short range vaporizer rectifying.
Step 2) after described the making with extra care, obtain highly purified neopentyl glycol and refined raffinate, because refined raffinate still contains a large amount of NPG except that containing organic salt, must reclaim, so the present invention is preferably further in step 2) add organic solvent in the refined raffinate that obtains, to separate and remove organic salt, the neopentyl glycol that reclaims is wherein returned step 1), recycle after merging with described hydrogenated products, to improve product yield.Described organic solvent is selected from Fatty Alcohol(C12-C14 and C12-C18) or ether or its mixture, the mixture of one or more in particular methanol, ethanol, propyl alcohol, butanols, ether or the methyl tertiary butyl ether; Most preferably methyl alcohol or butanols.
Compared with prior art, the beneficial effect of the inventive method is: by product is few, and quality product and yield are all higher, the purity of the neopentyl glycol that makes 〉=99.5%.Active nickel catalyst used in the present invention can carry out hydrogenation under lower temperature, preferred 60-80 ℃, therefore pressure-controlling greatly reduces the generation of ester impurity in the 1-5MPa scope; In addition and since this method in by product less relatively, so the saponification alkali number that uses lower, the NPG quality, the yield that obtain are all higher.In addition, the present invention reclaims means such as neopentyl glycol recycles after by alkali cleaning saponification, short distance rectifying and desalination neopentyl glycol is purified, and also can further improve product purity and productive rate.
Embodiment
Explain technical scheme of the present invention and effect in detail with the form of embodiment below, but the present invention is not limited to following examples.All relate to the numerical value of per-cent in following examples, except that specified otherwise, all refer to weight percent.
Embodiment 1. produces hydroxy pivalin aldehyde
In reactor, drop into isobutyric aldehyde 46.8g respectively, 37% formalin 42.2g, triethylamine 2.6g, stir and heat up, keep 70-90 ℃ of reaction 1-2hr, obtain hydroxy pivalin aldehyde, add solvent (methyl alcohol or butanols) dilution and prepare hydrogenation, this reaction process is according to the output size, but periodical operation also can be designed to operate continuously.
Embodiment 2 hydroxy pivalin aldehyde hydrogenation
Hydroxy pivalin aldehyde-methanol solution that embodiment 1 is obtained drops in the hydrogen pressure still, and the trade mark of adding 5% is the commercially available active nickel catalyst of SC3100, and under the hydrogen pressure of 3.5MPa, in 80 ℃ of reaction 2-3hr, the release blowing obtains hydrogenated products.
At the run duration of 100hr altogether, do not observe the tangible passivation of catalyzer.
The change such as the following table 1 of component before and after the step of hydrogenation:
Table 1
| Component | Before the step of hydrogenation (content %) | After the step of hydrogenation (content %) |
| Methyl alcohol | 35.42 | 35.09 |
| Isopropylcarbinol | 0.06 | 2.02 |
| Water | 6.31 | 6.23 |
| Isobutyric aldehyde | 2.29 | 0.35 |
| Triethylamine | 1.11 | 1.10 |
| Hydroxy pivalin aldehyde | 48.45 | - |
| Neopentyl glycol | 3.95 | 52.96 |
| DOPCP | 1.54 | 1.52 |
| Neopentyl glycol | 0.74 | 0.73 |
| Other materials | 0.13 |
Example 3, the hydroxy pivalin aldehyde hydrogenation
Hydroxy pivalin aldehyde-methanol solution that embodiment 1 is obtained drops in the hydrogen pressure still, and the trade mark of adding 5% is the commercially available active nickel catalyst of SC3100, and under the hydrogen pressure of 4.5MPa, in 70 ℃ of reaction 2-3hr, the release blowing obtains hydrogenated products.
At the run duration of 100hr altogether, do not observe the tangible passivation of catalyzer.
The change such as the following table 2 of component before and after the step of hydrogenation:
Table 2
| Component | Before the step of hydrogenation (content %) | After the step of hydrogenation (content %) |
| Methyl alcohol | 40.42 | 40.09 |
| Isopropylcarbinol | 0.06 | 2.02 |
| Water | 6.31 | 6.23 |
| Isobutyric aldehyde | 2.29 | 0.35 |
| Triethylamine | 1.11 | 1.10 |
| Hydroxy pivalin aldehyde | 43.45 | - |
| Neopentyl glycol | 3.95 | 47.96 |
| DOPCP | 1.54 | 1.52 |
| Neopentyl glycol | 0.74 | 0.73 |
| Other materials | 0.13 |
Example 4 hydroxy pivalin aldehyde hydrogenation
Hydroxy pivalin aldehyde-butanol solution that embodiment 1 is obtained drops in the hydrogen pressure still, and the trade mark of adding 10% is the commercially available active nickel catalyst of SC3100, and under the hydrogen pressure of 4.5MPa, in 60 ℃ of reaction 2-3hr, the release blowing obtains hydrogenated products.
At the run duration of 100hr altogether, do not observe the tangible passivation of catalyzer.
The change such as the following table 3 of component before and after the step of hydrogenation:
Table 3
| Component | Before the step of hydrogenation (content %) | After the step of hydrogenation (content %) |
| Methyl alcohol | 45.42 | 45.09 |
| Isopropylcarbinol | 0.06 | 2.02 |
| Water | 6.31 | 6.23 |
| Isobutyric aldehyde | 2.29 | 0.35 |
| Triethylamine | 1.11 | 1.10 |
| Hydroxy pivalin aldehyde | 38.45 | - |
| Neopentyl glycol | 3.95 | 42.96 |
| DOPCP | 1.54 | 1.52 |
| Neopentyl glycol | 0.74 | 0.73 |
| Other materials | 0.13 |
Solvent is reclaimed in embodiment 5 hydrogenated products saponification
The sodium hydroxide of adding 5% in the hydrogenated products that embodiment 2 obtains, the intensification precipitation reclaims methyl alcohol, and DOPCP (HPNE) and neopentyl glycol (TMPD) wherein handled in saponification simultaneously, obtains the thick product of neopentyl glycol.
The change of component such as following table 4 after the saponification precipitation step:
Table 4
| Water component behind the saponification precipitation | Neopentyl glycol | Water | Low-boiling-point substance | TMPD | HPNE | Sodium salt |
| Quality % | 66.04 | 28.71 | 2.35 | 0.1 | - | 2.8 |
Solvent is reclaimed in embodiment 6 hydrogenated products saponification
The sodium hydroxide of adding 5% in the hydrogenated products that embodiment 4 obtains, the intensification precipitation reclaims butanols, and DOPCP (HPNE) and neopentyl glycol (TMPD) wherein handled in saponification simultaneously, obtains the thick product of neopentyl glycol.
The change of component such as following table 5 after the saponification precipitation step:
Table 5
| Water component behind the saponification precipitation | Neopentyl glycol | Water | Low-boiling-point substance | TMPD | HPNE | Sodium salt |
| Quality % | 66.02 | 28.69 | 2.37 | 0.1 | - | 3.0 |
Embodiment 7 purification neopentyl glycol
The thick product aqueous solution of neopentyl glycol behind the saponification precipitation among the embodiment 5 is sent in the two-stage short-path evaporator, the first step is sloughed the water in the mixed solution, enter the second stage and distill a large amount of neopentyl glycol of purifying out, promptly obtain highly purified neopentyl glycol product, quality sees the following form 6:
Table 6
| Product is formed | Neopentyl glycol | Water | Low-boiling-point substance | TMPD | Other materials |
| Quality % | 99.55 | 0.15 | 0.05 | 0.2 | 0.05 |
Refined raffinate enters the dissolution kettle that methyl alcohol is housed in advance, and filter at low temperature is removed organic salt, and filtrate collection is stand-by.
The recycling of embodiment 8 refined raffinates
Reclaim the filtrate that refined raffinate obtains among the embodiment 7 behind desalination, return embodiment 3, merge, add 10% sodium hydroxide with the hydrogenated products that obtains, the intensification precipitation reclaims methyl alcohol, and DOPCP (HPNE) and neopentyl glycol (TMPD) wherein handled in saponification simultaneously.
The change of component such as following table 7 after the saponification precipitation step:
Table 7
| Water component behind the saponification precipitation | Neopentyl glycol | Water | Low-boiling-point substance | TMPD | HPNE | Sodium salt |
| Quality % | 66.00 | 28.72 | 2.35 | 0.1 | - | 3.1 |
Solution behind the above-mentioned saponification precipitation is sent in the two-stage short-path evaporator, and the first step is sloughed water in the mixed solution, enters the second stage and distills a large amount of neopentyl glycol of purifying out, promptly obtains highly purified neopentyl glycol product, quality such as following table 8:
Table 8
| Product is formed | Neopentyl glycol | Water | Low-boiling-point substance | TMPD | Other materials |
| Quality % | 99.56 | 0.14 | 0.05 | 0.21 | 0.04 |
The clout that distillation is purified can also enter the dissolution kettle that methyl alcohol or butanols are housed in advance once more, and filter at low temperature after removing organic salt recycles the process of filtrate according to present embodiment.
Can clearly be seen that from above embodiment,, can produce highly purified neopentyl glycol economically according to the present invention.
Claims (10)
1. the preparation method of a neopentyl glycol comprises the steps:
1) use active nickel catalyst under 60 ℃～80 ℃ temperature and the pressure of 1-5MPa, in the presence of organic solvent, hydroxy pivalin aldehyde is carried out hydrogenation, hydrogenated products re-uses mineral alkali and carries out saponification, obtains the thick product of neopentyl glycol;
2) the thick product of neopentyl glycol that step 1) is obtained is made with extra care, and obtains highly purified neopentyl glycol and refined raffinate.
2. the described method of claim 1, it is characterized in that: the described organic solvent of step 1) is selected from Fatty Alcohol(C12-C14 and C12-C18) or ether or its mixture; The mixture of one or more in particular methanol, ethanol, propyl alcohol, butanols, ether or the methyl tertiary butyl ether.
3. the described method of claim 1 is characterized in that: the described active nickel catalyst of step 1) is the active nickel catalyst through molybdenum, iron and chromium modification.
4. the described method of claim 1, it is characterized in that: condensation under tertiary amine catalyst catalysis obtains the described hydroxy pivalin aldehyde of step 1) by formaldehyde and isobutyric aldehyde.
5. the described method of claim 1, it is characterized in that: the described mineral alkali of step 1) is a sodium hydroxide.
6. the described method of claim 1 is characterized in that: step 2) the described refining ultra-short range vaporizer rectifying that is to use.
7. the described method of claim 1 is characterized in that: further in step 2) add organic solvent in the refined raffinate that obtains, to separate and remove organic salt, the neopentyl glycol that reclaims is wherein returned step 1), recycles after merging with described hydrogenated products.
8. the described method of claim 7, it is characterized in that: described organic solvent is selected from Fatty Alcohol(C12-C14 and C12-C18) or ether or its mixture.
9. the described method of claim 7 is characterized in that: described organic solvent is selected from one or more the mixture in methyl alcohol, ethanol, propyl alcohol, butanols, ether or the methyl tertiary butyl ether.
10. the described method of claim 9, it is characterized in that: described organic solvent is methyl alcohol or butanols.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351647A (en) * | 2011-07-29 | 2012-02-15 | 淇县彤邦化工有限公司 | Novel process for recycling steam condensate |
| CN103962141A (en) * | 2014-05-18 | 2014-08-06 | 华东理工大学 | Catalyst for synthesizing neopentyl glycol from hydroxypivalaldehyde by virtue of hydrogenation |
| CN107311840A (en) * | 2017-07-17 | 2017-11-03 | 衡阳屹顺化工有限公司 | A kind of production technology of neopentyl glycol |
| CN107337595A (en) * | 2017-07-12 | 2017-11-10 | 海门华祥医药科技有限公司 | The synthesis technique of cyclopentyl phenyl ketone |
| CN107540521A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The method of hydroxy pivalin aldehyde Hydrogenation neopentyl glycol |
| CN112142565A (en) * | 2020-09-18 | 2020-12-29 | 万华化学集团股份有限公司 | Neopentyl glycol refining and ester removing method and device system with low energy consumption |
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|---|---|---|---|---|
| CN1234017A (en) * | 1996-10-22 | 1999-11-03 | 株式会社Lg化学 | Process for continuous prodn. of neopentyl glycol |
| CN1286673A (en) * | 1997-12-30 | 2001-03-07 | 奈斯特化学公司 | Process for preparation of neopentyl glycol |
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2010
- 2010-11-03 CN CN2010105311901A patent/CN101993351A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234017A (en) * | 1996-10-22 | 1999-11-03 | 株式会社Lg化学 | Process for continuous prodn. of neopentyl glycol |
| CN1286673A (en) * | 1997-12-30 | 2001-03-07 | 奈斯特化学公司 | Process for preparation of neopentyl glycol |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351647A (en) * | 2011-07-29 | 2012-02-15 | 淇县彤邦化工有限公司 | Novel process for recycling steam condensate |
| CN103962141A (en) * | 2014-05-18 | 2014-08-06 | 华东理工大学 | Catalyst for synthesizing neopentyl glycol from hydroxypivalaldehyde by virtue of hydrogenation |
| CN107540521A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The method of hydroxy pivalin aldehyde Hydrogenation neopentyl glycol |
| CN107337595A (en) * | 2017-07-12 | 2017-11-10 | 海门华祥医药科技有限公司 | The synthesis technique of cyclopentyl phenyl ketone |
| CN107311840A (en) * | 2017-07-17 | 2017-11-03 | 衡阳屹顺化工有限公司 | A kind of production technology of neopentyl glycol |
| CN112142565A (en) * | 2020-09-18 | 2020-12-29 | 万华化学集团股份有限公司 | Neopentyl glycol refining and ester removing method and device system with low energy consumption |
| CN112142565B (en) * | 2020-09-18 | 2022-08-05 | 万华化学集团股份有限公司 | Neopentyl glycol refining and ester removing method and device system with low energy consumption |
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Application publication date: 20110330 |