CN1122014C - Technological process of raising yield and purity of synthetic methyl vinyl ketone - Google Patents
Technological process of raising yield and purity of synthetic methyl vinyl ketone Download PDFInfo
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- CN1122014C CN1122014C CN 00133038 CN00133038A CN1122014C CN 1122014 C CN1122014 C CN 1122014C CN 00133038 CN00133038 CN 00133038 CN 00133038 A CN00133038 A CN 00133038A CN 1122014 C CN1122014 C CN 1122014C
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- pyranton
- acetone
- alcohol
- water
- cymogene
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a technological process for increasing the synthesis yield and the purity of methyl vinyl ketone. Crude butanolone is prepared by a conventional technological process and is mixed with water as an azeotropic agent, the mixture in introduced into an azeotrope tower, and an azeotrope of diacetone alcohol and water is distilled off; the azeotrope is salted out with strong brine, the upper layer is recovered diacetone alcohol, and the lower layer is weak brine; after a part of water is distilled off, the weak brine becomes strong brine and is returned to a demixer; butanolone with removed diacetone alcohol is added with a catalyst for dehydration, the distillate is crude water-bearing methyl vinyl ketone, and the crude methyl vinyl ketone is dried and distilled to obtained the finished methyl vinyl ketone product. In the present invention, through removing diacetone alcohol in a reaction liquid and adding recovered diacetone alcohol in the synthetic process of butanolone to inhibit the formation of diacetone alcohol, the synthesis yield and the purity of methyl vinyl ketone are increased, and the production of three wastes is reduced.
Description
In methylene acetone is synthetic, processing method commonly used as shown in Figure 1, be with acetone, formaldehyde in the presence of the basic solutions such as NaOH or KOH in reactor after the reaction, neutralize with oxalic acid solution, enter and take off the acetone tower, the acetone that reclaims can be recycled, and solution cymogene keto-alcohol enters dehydration generation methylene acetone in the dehydration still.The problem that this method exists is: when butanone alcohol is synthetic, produce the by product Pyranton inevitably, then form mesityl oxide after the dehydration, this not only makes acetone consumption increase, also make simultaneously the purity of methylene acetone crude product descend, bring certain degree of difficulty for follow-up methylene acetone treating process, and increased the quantity of the by product that becomes " three wastes ".
The purpose of this invention is to provide the Pyranton that a kind of removal forms and in butanone alcohol building-up process, add in reaction and reclaim Pyranton and suppress Pyranton and form, thereby improve the processing method of methylene acetone synthesis yield and purity.
In order to achieve the above object, the present invention takes following processing method, after acetone, formaldehyde, alkaline aqueous solution are reacted in reactor, with the oxalic acid solution neutralization, enters and takes off the acetone tower, makes the cymogene keto-alcohol.Again the cymogene keto-alcohol is added and enter azeotropic distillation column after entrainer water mixes, steam the azeotrope of Pyranton and water, azeotrope is after strong brine is saltoutd, tell the upper strata for reclaiming Pyranton, lower floor is a weak brine, and steaming becomes strong brine after the portion water and return quantizer again, and the butanone alcohol that has taken off Pyranton adds the acid catalyst dehydration, overhead product is aqueous cymogene ketenes, the dry redistillation of the cymogene ketenes methylene acetone that gets product.The Pyranton that reclaims mixes with acetone as butanone alcohol synthesis reaction raw material, with the generation of Pyranton in the inhibited reaction process.
Advantage of the present invention is:
1) will react the by product Pyranton and before dehydration, separate, improve the purity of dehydration back methylene acetone crude product;
2) the by product Pyranton is made full use of the generation that suppresses to pay reaction, reduced acetone unit consumption and methylene acetone synthetic cost;
3) reduced the generation of " three wastes ", made this technology more meet environmental protection requirement.
Below in conjunction with drawings and Examples the present invention is described in detail.
Fig. 1 is former process flow sheet;
Fig. 2 is a process flow sheet of the present invention.
As shown in Figure 2, with acetone, formaldehyde is after reacting in reactor A in the presence of the basic solution, neutralize with oxalic acid solution, enter and take off acetone tower B, make the cymogene keto-alcohol, with the cymogene keto-alcohol with enter azeotropic distillation column C after entrainer water mixes, steam the azeotrope of Pyranton and water, azeotrope is told the upper strata for reclaiming Pyranton after strong brine is saltoutd, lower floor is a weak brine, steaming becomes strong brine after the portion water and returns quantizer again, the butanone alcohol that has taken off Pyranton adds the acid catalyst dehydration, and overhead product is aqueous cymogene ketenes, the dry redistillation of the cymogene ketenes methylene acetone that gets product.The Pyranton that reclaims mixes with acetone as butanone alcohol synthesis reaction raw material, and with the generation of Pyranton in the inhibited reaction process, thereby the yield of raising butanone alcohol synthesis reaction reduces the generation of " three wastes ".
The above-mentioned entrainer water yield is 6～12 times of Pyranton amount in the cymogene keto-alcohol; The used salt of saltouing is NaCl, CaCl
2, NaNO
3, a kind of or any 2～4 kinds of salt among the KCl mixture.
To get butanone alcohol crude product behind institute's synthetic butanone alcohol reaction solution recovery acetone, its composition is mainly the pure and mild Pyranton of butanone.Utilize Pyranton to form azeotropic butanone alcohol with water and then do not form the azeotropic characteristics with water, with adding water in the crude product butanone alcohol Pyranton is steamed with the water azeotropic, the Pyranton in the distillate reclaims with the back layering of saltouing.The butanone alcohol of removing Pyranton adds the catalyzer dehydration and promptly obtains content and reach methylene acetone more than 97%.
The Pyranton that reclaims mixes with acetone, utilizes the reversible reaction that exists between the acetone and Pyranton under the alkaline condition to suppress the generation of Pyranton, thus the utilization ratio of raising acetone.
Reaction result of the present invention is as shown in table 1:
| Embodiment | Acetone/formaldehyde (mol ratio) | Temperature of reaction (℃) | Reaction times (min) | Methylene acetone yield (%) | Crude product methylene acetone content (dry back) (%) |
| 1 | 15 | 30 | 15 | 70.2 | 97.2 |
| 2 | 20 | 30 | 12 | 72.4 | 97.7 |
| 3 | 30 | 25 | 18 | 73.1 | 97.5 |
Comparative example reaction and result are as shown in table 2:
| Comparative example | Acetone/formaldehyde (mol ratio) | Temperature of reaction (℃) | Reaction times (min) | Methylene acetone yield (%) | Crude product methylene acetone content (dry back) (%) |
| 1 | 15 | 30 | 15 | 54.4 | 82.1 |
| 2 | 20 | 30 | 12 | 56.2 | 80.4 |
| 3 | 30 | 25 | 18 | 57.6 | 78.9 |
Claims (3)
1. processing method that improves methylene acetone synthesis yield and purity, with acetone, formaldehyde, after alkaline aqueous solution reacts in reactor [A], neutralize with oxalic acid solution, enter and take off acetone tower [B], make the cymogene keto-alcohol, it is characterized in that: enter azeotropic distillation column [C] after the cymogene keto-alcohol is added the mixing of entrainer water, steam the azeotrope of Pyranton and water, azeotrope is told the upper strata for reclaiming Pyranton after strong brine is saltoutd, lower floor is a weak brine, steaming becomes strong brine after the portion water and returns quantizer again, the butanone alcohol that has taken off Pyranton adds the acid catalyst dehydration, and overhead product is aqueous cymogene ketenes, the dry redistillation of the cymogene ketenes methylene acetone that gets product; The Pyranton that reclaims mixes with acetone as butanone alcohol synthesis reaction raw material, and with the generation of Pyranton in the inhibited reaction process, thereby the yield of raising butanone alcohol synthesis reaction reduces the generation of " three wastes ".
2. a kind of processing method that improves methylene acetone synthesis yield and purity according to claim 1 is characterized in that: the entrainer water yield is 6～12 times of Pyranton amount in the cymogene keto-alcohol.
3. a kind of processing method that improves methylene acetone synthesis yield and purity according to claim 1 is characterized in that: the used salt of saltouing is NaCl, CaCl
2, NaNO
3, a kind of or any 2～4 kinds of salt among the KCl mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00133038 CN1122014C (en) | 2000-11-17 | 2000-11-17 | Technological process of raising yield and purity of synthetic methyl vinyl ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00133038 CN1122014C (en) | 2000-11-17 | 2000-11-17 | Technological process of raising yield and purity of synthetic methyl vinyl ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1297880A CN1297880A (en) | 2001-06-06 |
| CN1122014C true CN1122014C (en) | 2003-09-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00133038 Expired - Lifetime CN1122014C (en) | 2000-11-17 | 2000-11-17 | Technological process of raising yield and purity of synthetic methyl vinyl ketone |
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| CN (1) | CN1122014C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633611B (en) * | 2012-03-28 | 2014-04-16 | 南开大学 | Method of using modified alumina catalyst to continuously prepare methyl vinyl ketone |
| CN105056660B (en) * | 2015-07-27 | 2016-11-30 | 北京时代浩鼎科技股份有限公司 | A kind of air cleaner |
| CN105056643B (en) * | 2015-07-27 | 2017-01-04 | 宁波智通环保科技有限公司 | A kind of with electronic-controlled installation with the air cleaner of air intake valve |
| CN106699531A (en) * | 2016-12-13 | 2017-05-24 | 厦门金达威维生素有限公司 | Method for preparing methyl vinyl ketone through continuous dehydration of butanone alcohol |
| CN109516906B (en) * | 2018-11-29 | 2021-10-08 | 厦门金达威维生素有限公司 | Method and device for synthesizing butanol through catalytic reaction rectification |
-
2000
- 2000-11-17 CN CN 00133038 patent/CN1122014C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1297880A (en) | 2001-06-06 |
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Owner name: ZHEJIANG XINHECHENG CO., LTD. SHANGYU XINHECHENG B Free format text: FORMER OWNER: ZHEJIANG XINHECHENG CO., LTD. Effective date: 20120301 |
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Effective date of registration: 20120301 Address after: Hangzhou City, Zhejiang province 310027 Ancient Jade Road 20 Co-patentee after: Zhejiang Xinhecheng Co., Ltd. Patentee after: Zhejiang University Co-patentee after: Shangyu Xinhecheng Bio-Chemical Co., Ltd. Co-patentee after: Zhejiang NHU Pharmaceutical Co., Ltd. Address before: Hangzhou City, Zhejiang province 310027 Ancient Jade Road 20 Co-patentee before: Zhejiang Xinhecheng Co., Ltd. Patentee before: Zhejiang University |
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