CN113200834A - Method for preparing hydroxypivalaldehyde - Google Patents
Method for preparing hydroxypivalaldehyde Download PDFInfo
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- CN113200834A CN113200834A CN202110530590.9A CN202110530590A CN113200834A CN 113200834 A CN113200834 A CN 113200834A CN 202110530590 A CN202110530590 A CN 202110530590A CN 113200834 A CN113200834 A CN 113200834A
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- Prior art keywords
- reactor
- reaction
- hydroxypivalaldehyde
- circulating water
- heat exchangers
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- JJMOMMLADQPZNY-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanal Chemical compound OCC(C)(C)C=O JJMOMMLADQPZNY-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 10
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000007859 condensation product Substances 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000002826 coolant Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000013021 overheating Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 hydroxyl pivalic aldehyde Chemical compound 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- 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
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The invention provides a method for preparing hydroxypivalaldehyde, which comprises the following steps: s1 mixing formaldehyde, isobutyraldehyde and an organic amine liquid catalyst, introducing the mixture into a reactor for condensation reaction, wherein the reactor is provided with a plurality of built-in heat exchangers which are symmetrically distributed around the reactor, a top-in tube or coil is adopted, and a multi-layer paddle type stirrer is arranged at the axis of the reactor; s2, the condensation product enters a rectifying tower for vacuum rectification to obtain the hydroxypivalaldehyde. The heat exchangers are respectively supplied with circulating water for cooling, and the temperature rise of the circulating water is controlled so as to achieve the purpose of uniform heat exchange. The central part is provided with a multi-layer paddle stirrer to strengthen heat transfer and mix materials. The invention ensures that the raw materials entering the reactor are quickly dispersed, the reaction heat is quickly removed, and the local overheating caused by overhigh concentration of reactants and violent reaction is avoided. The method can control the reaction temperature to be 68-72 ℃, so that the selectivity of the hydroxypivalaldehyde is improved by more than 1 percent, and the benefit is remarkable.
Description
Technical Field
The invention belongs to the technical field of chemical intermediate production, and particularly relates to a method for preparing hydroxypivalaldehyde.
Background
Formaldehyde and isobutyraldehyde are subjected to condensation reaction under alkaline conditions to produce hydroxyl pivalic aldehyde and neopentyl glycol. The reaction is a heat-releasing liquid phase homogeneous reaction, the reaction temperature is strictly controlled, and the optimal reaction temperature is controlled between 68 and 72 ℃. In the reaction process, local overheating is easily caused due to overhigh concentration of reactants and violent reaction, so that the number of byproducts is increased, the product yield is reduced, and the loss of the catalyst is increased.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for accurately controlling the temperature in the process of preparing hydroxypivalaldehyde, which comprises the following steps:
s1, mixing formaldehyde, isobutyraldehyde and an organic amine liquid catalyst, and introducing the mixture into a reactor for condensation reaction; the reactor is provided with a plurality of built-in heat exchangers which are symmetrically distributed around the reactor, the built-in heat exchangers adopt top-in tubes or coil pipes, and the axis of the reactor is provided with a multilayer paddle type stirrer;
s2, the condensation product enters a rectifying tower for vacuum rectification to obtain the hydroxypivalaldehyde.
The inlet of the tube array or the coil pipe is connected with the cooling medium inlet through the inlet pipe, and the outlet of the tube array or the coil pipe is connected with the cooling medium outlet through the outlet pipe.
To simplify the reactor structure, the inlet and outlet of the tubes or coils are arranged at the top of the reactor.
The cooling medium is constant-temperature circulating water, and the temperature rise of the circulating water is controlled to achieve the purpose of uniform heat exchange; furthermore, the reaction temperature is accurately controlled between 68 ℃ and 72 ℃ by adjusting the flow rate of circulating water in the tube array or the coil pipe, and the reaction pressure is controlled between 0.1 MPaG and 0.6MPaG by pressure control. Under the accurate and stable reaction conditions, the condensation reaction obtains the best conversion rate and selectivity.
The feeding proportion of the condensation reaction is as follows: isobutyraldehyde is 1.04-1.2: 1 (molar ratio), wherein the feeding amount of the organic amine used as the catalyst is 1-3% of the total feeding amount. The organic amine liquid catalyst is aliphatic amine, and further is trimethylamine, diethylamine or tripropylamine.
The invention has the advantages that each heat exchanger is respectively supplied with circulating water for cooling, and the temperature rise of the circulating water is controlled to achieve the purpose of uniform heat exchange. The central part is provided with a multi-layer paddle stirrer to strengthen heat transfer and mix materials. The invention can quickly disperse the raw materials (the mixture of formaldehyde, isobutyraldehyde and organic amine liquid catalyst) entering the reactor, quickly remove the reaction heat release and avoid local overheating caused by overhigh concentration of reactants and violent reaction. The method can control the reaction temperature to be 68-72 ℃, so that the selectivity of the hydroxypivalaldehyde is improved by more than 1 percent, and the benefit is remarkable.
Drawings
FIG. 1 is a schematic view of the structure of a reactor in a condensation reaction,
wherein, 1 is feeding, 2 is condensation product, 3 is built-in heat exchanger, 4 is circulating water, and 5 is multilayer paddle agitator.
Detailed Description
Example 1
A process for preparing hydroxypivalaldehyde comprising the steps of:
s1 introducing 115kg of formaldehyde with the concentration of 37%, 100kg of isobutyraldehyde with the concentration of 99.5% and 3kg of trimethylamine with the purity of 99.3% into a reactor for condensation reaction;
the reactor is provided with 6 built-in heat exchangers 3, the built-in heat exchangers 3 are symmetrically distributed on the periphery of the reactor, the built-in heat exchangers 3 adopt top-in tubes, and the axis of the reactor is provided with a multilayer paddle type stirrer 5; the inlet of the tube array is connected with the inlet of circulating water 4 through an inlet pipe, the outlet of the tube array is connected with the outlet of the circulating water 4 through an outlet pipe, and the circulating water is hot water at 55 +/-1.5 ℃; fresh raw materials enter the lower part of the reactor, and a discharge hole is positioned at the upper part of the reactor; the reaction temperature is controlled to be 70 +/-1.5 ℃ by adjusting the flow rate of circulating water in the tube array, the reaction pressure is stabilized at 0.25MPaG by adopting nitrogen, the stirring speed is 60-100 rpm, the liquid phase composition is analyzed by sampling after the reaction is carried out for 1 hour and 45 minutes, the conversion rate of isobutyraldehyde is 93.95 percent, and the selectivity of a target product, namely hydroxyl pivalic aldehyde and neopentyl glycol, reaches 94.83 percent.
S2, the condensation product 2 enters an aldehyde recovery tower to be rectified under normal pressure, unreacted isobutyraldehyde, trimethylamine and the like are recovered at the tower top and returned to the condensation reactor to react again, and the material at the tower bottom is hydroxyl pivalic aldehyde aqueous solution which can be used as a hydrogenation raw material to prepare neopentyl glycol.
Through the recovery of aldehyde, the total conversion rate of isobutyraldehyde can reach more than 98 percent.
Example 2
A full-mixing kettle type reactor with stirring is adopted, four groups of U-shaped tubular cooling tube groups are arranged in the reactor, and a cooling medium is hot water with the temperature of 55 +/-1.5 ℃. 115kg of formaldehyde with the concentration of 37%, 100kg of isobutyraldehyde with the concentration of 99.5% and 3kg of trimethylamine with the purity of 99.3% were added to the lower part of the reactor. The reaction temperature is controlled to be 70 +/-1.5 ℃ by adjusting the flow of circulating water, the reaction pressure is stabilized at 0.25MPaG by adopting nitrogen, and the liquid phase composition is analyzed by sampling after the reaction is carried out for 1 hour and 45 minutes, wherein the typical composition is as follows: 58.3 percent of hydroxyl pivalaldehyde, 2.75 percent of isobutyraldehyde, 0.32 percent of formaldehyde and 1.15 percent of trimethylamine. Accordingly, the conversion rate of isobutyraldehyde is calculated to be 93.95%, and the selectivity of the target product, namely hydroxyl pivalic aldehyde and neopentyl glycol, reaches 94.83%. The reaction effect is obviously higher than that of the reported conventional condensation reaction by about two percentage points.
Example 3
The same as example 1, but 2 to 3 reactors are arranged in series for operation in step S1, the residence time in the reaction process is controlled to be 3 hours, and the conversion per pass of isobutyraldehyde can reach 92 to 95%.
Claims (5)
1. A method for preparing hydroxypivalaldehyde, which is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing formaldehyde, isobutyraldehyde and an organic amine liquid catalyst, and introducing the mixture into a reactor for condensation reaction; the reactor is provided with a plurality of built-in heat exchangers (3), the built-in heat exchangers (3) are symmetrically distributed around the reactor, the built-in heat exchangers (3) adopt top-in tubes or coil pipes, and the axis of the reactor is provided with a multilayer paddle type stirrer (5);
s2, the condensation product enters a rectifying tower for vacuum rectification to obtain the hydroxypivalaldehyde.
The inlet of the tube array or the coil pipe is connected with the cooling medium inlet through the inlet pipe, and the outlet of the tube array or the coil pipe is connected with the cooling medium outlet through the outlet pipe.
2. A process for preparing hydroxypivalaldehyde according to claim 1, wherein: the cooling medium is constant temperature circulating water (4), and the temperature rise of the circulating water is controlled to achieve the purpose of uniform heat exchange.
3. A process for preparing hydroxypivalaldehyde according to claim 2, wherein: the reaction temperature is accurately controlled to be 68-72 ℃ by adjusting the flow rate of circulating water, and the reaction pressure is controlled to be 0.1-0.6 MPaG by pressure control.
4. A process for preparing hydroxypivalaldehyde according to claim 1, wherein: formaldehyde: the molar ratio of isobutyraldehyde is 1.04-1.2: 1, the feeding amount of the organic amine liquid is 1-3% of the total feeding amount.
5. A process for preparing hydroxypivalaldehyde according to claim 1, wherein: the organic amine liquid catalyst is aliphatic amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110530590.9A CN113200834A (en) | 2021-05-15 | 2021-05-15 | Method for preparing hydroxypivalaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110530590.9A CN113200834A (en) | 2021-05-15 | 2021-05-15 | Method for preparing hydroxypivalaldehyde |
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| Publication Number | Publication Date |
|---|---|
| CN113200834A true CN113200834A (en) | 2021-08-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110530590.9A Pending CN113200834A (en) | 2021-05-15 | 2021-05-15 | Method for preparing hydroxypivalaldehyde |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07215904A (en) * | 1994-02-03 | 1995-08-15 | Sumitomo Chem Co Ltd | Production of hydroxypivalaldehyde |
| CN102212080A (en) * | 2010-04-12 | 2011-10-12 | 中国科学院过程工程研究所 | Reaction device for preparing methyl chlorosilane and reaction system comprising same |
| WO2012143309A1 (en) * | 2011-04-19 | 2012-10-26 | Basf Se | Method for producing neopentyl glycol |
| US8710278B1 (en) * | 2013-01-31 | 2014-04-29 | Eastman Chemical Company | Process for producing polyols |
| CN105061170A (en) * | 2015-09-08 | 2015-11-18 | 上海华谊（集团）公司 | Method for preparing hydroxy neovaleraldehyde |
| CN111620767A (en) * | 2020-07-02 | 2020-09-04 | 中国天辰工程有限公司 | Method for improving selectivity of aldol condensation reaction |
-
2021
- 2021-05-15 CN CN202110530590.9A patent/CN113200834A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07215904A (en) * | 1994-02-03 | 1995-08-15 | Sumitomo Chem Co Ltd | Production of hydroxypivalaldehyde |
| CN102212080A (en) * | 2010-04-12 | 2011-10-12 | 中国科学院过程工程研究所 | Reaction device for preparing methyl chlorosilane and reaction system comprising same |
| WO2012143309A1 (en) * | 2011-04-19 | 2012-10-26 | Basf Se | Method for producing neopentyl glycol |
| US8710278B1 (en) * | 2013-01-31 | 2014-04-29 | Eastman Chemical Company | Process for producing polyols |
| CN105061170A (en) * | 2015-09-08 | 2015-11-18 | 上海华谊（集团）公司 | Method for preparing hydroxy neovaleraldehyde |
| CN111620767A (en) * | 2020-07-02 | 2020-09-04 | 中国天辰工程有限公司 | Method for improving selectivity of aldol condensation reaction |
Non-Patent Citations (2)
| Title |
|---|
| 刘齐琼等: "羟基新戊醛合成工艺及其动力学", 《化学反应工程与工艺》 * |
| 宋连珍: "《制药过程原理及设备》", 31 January 2013, 中国医药科技出版社 * |
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Application publication date: 20210803 |
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