CN1239457C - Separation method for equatic mixture of formic acid and acetic acid - Google Patents
Separation method for equatic mixture of formic acid and acetic acid Download PDFInfo
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- CN1239457C CN1239457C CN 01108268 CN01108268A CN1239457C CN 1239457 C CN1239457 C CN 1239457C CN 01108268 CN01108268 CN 01108268 CN 01108268 A CN01108268 A CN 01108268A CN 1239457 C CN1239457 C CN 1239457C
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- water
- formic acid
- entrainer
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Abstract
The present invention relates to a method for separating hydrous mixtures of formic acid and acetic acid. An entrainer is added in the mixture, and is rectified to carry out azeotropic dehydration, and the water content of the kettle liquid is below 2% after dehydration. The kettle liquid is rectified into a light component, a transition fraction and the finished acetic acid. The water is separated from the water phase collected in the dehydration process by a water separator, and the entrainer is recovered. The light component and the transition fraction in the rectifying process are added in the next batch of mixtures to be processed together. The purity of the recovered acetic acid can achieve more than 99% after being processed by the method of the present invention, and the economical benefits and the social benefits are obvious.
Description
Technical field
The present invention relates to the separation method of formic acid, acetate.
Background technology
Organic nitration mixture (formic acid, acetate aqueous mixture) is the by product that acetic acid is produced in the acetaldehyde direct oxidation.At present, this mixture is in direct operational phase, is mainly used in to make water-resisting agent, low separant etc., and range of application is wideless, and cheap.Produce 1140 tons of formic acid, acetate aqueous mixture every year approximately in 70,000 tons of acetic acid plant production processes of one cover, formic acid content about 5-17%, acetic acid content about 62-80%, if carry out formic acid, separated from acetic acid makes basic chemical raw materials acetate and formic acid, will produce very big benefit.
Summary of the invention
The purpose of this invention is to provide the separation of a kind of formic acid, acetate aqueous mixture, obtain the method for formic acid and acetate.
Technical scheme of the present invention is as follows:
The separation method of a kind of formic acid, acetate aqueous mixture, it comprises the following steps:
(1) add the entrainer ethyl acetate in formic acid, acetate aqueous mixture, place rectifying tower water trap rectifying azeotropic dehydration, the content of residuary water is 1.38-1.99 weight % in the dehydration tower bottoms,
(2) the dehydration tower bottoms that is 1.38-1.99 weight % with the middle water content of step (1) places separating rectification tower to carry out rectifying, be divided into three cuts: light constituent, collecting tower top temperature is 97.0-101.8 ℃ of cut, interim fraction, collecting tower top temperature is 101.9-116.0 ℃ of cut, finished product acetate is collected 116.1-118.0 ℃ of cut of tower top temperature
(3) collect the middle isolated water of water trap of using of step (1),, reclaim entrainer again through rectifying,
(4) collect smart distilled light constituent and interim fraction in the step (2), repeat step (1) operation again in adding next batch formic acid, the acetate aqueous mixture.
Major advantage of the present invention:
(1) mixture that produces water-containing formic acid, acetate in the acetic acid plant production process carries out formic acid, separated from acetic acid, makes basic chemical raw materials acetate and formic acid.70,000 tons of acetic acid plants of one cover are produced 1140 tons of meters of nitration mixture per year, and this finished product acetate produces 636 tons approximately, and purity can be sold greater than 99%.
(2) the dehydration water is through reclaiming entrainer, and the entrainer rate of recovery is 91.5%, and the entrainer in the discharge water is 0.68%, and the CODcr value is 8.82 * 10
3Mg/l, this strand waste water can directly enter Sewage treatment systems and handle.
(3) adopt method less investment of the present invention, energy consumption is low, and used equipment is simple, the acetic acid yield height, and in sum, method of the present invention is that economic benefit or social benefit are all very obvious.
Embodiment
Further set forth the present invention with example below.
Embodiment 1
Add formic acid, acetate aqueous mixture (selecting the nitration mixture of 7 batches of different moisture contents in the process of the test) and entrainer ethyl acetate at dehydration Tata still as raw material, heating, after vapour-liquid reaches balance in the tower, total reflux 2-3 hour, during control cat head temperature t≤70.4 ℃, distillate adopts water trap water phase separated and ester mutually, collects water, and ester returns at the bottom of the still mutually.Each band water is about 9%, and dehydration so repeatedly is till the water in still liquid can not be taken out of.Steam remaining ester.Still liquid carries out formic acid, separated from acetic acid after collecting.Dehydration results sees Table 1.
Dehydration results shows: water content difference in the charging nitration mixture, and behind azeotropic dehydration, the content of residuary water is relatively stable in the dehydration still liquid, less than 2%, is 1.38-1.99%, average dehydration 84.2%; In the azeotropic dehydration process, impurity also part is removed, and dehydration back still liquid foreign matter content is less than 1.5%, and the content of formic acid, acetate is improved accordingly in the still liquid of dehydration back simultaneously.Be formic acid, separated from acetic acid, purifying acetic acid has been created condition.
Embodiment 2
The rectifying tower bottoms that will dewater adds the separating rectification tower still, and heating is after vapour-liquid reaches balance in the tower, total reflux 2-3 hour, the control tower top temperature is 97.0-101.8 ℃ and collects light constituent that the control tower top temperature is 101.9-116.0 ℃ and collects interim fraction that separating resulting sees Table 2.
Table 1 dehydration test data sheet (m/m, * 10
-2)
| Sequence number | Water | Formic acid | Acetate | Impurity | Entrainer | Weight in grams | Dehydration rate | |
| 1 | Charging | 6.62 | 5.35 | 59.1 | 2.41 | 26.5 | 750 | 79.0 |
| Water | 89.6 | 3.60 | 6.74 | 37 | ||||
| Entrainer | 3.55 | 4.93 | 91.5 | 177 | ||||
| Still liquid | 1.99 | 7.49 | 82.5 | 1.50 | 6.52 | 536 | ||
| 2 | Charging | 7.41 | 12.8 | 58.2 | 2.09 | 19.5 | 810 | 81.5 |
| Water | 84.9 | 8.22 | 6.87 | 51 | ||||
| Entrainer | 3.78 | 4.05 | 92.1 | 148 | ||||
| Still liquid | 1.81 | 17.0 | 77.1 | 1.10 | 2.99 | 611 | ||
| 3 | Charging | 17.5 | 7.63 | 48.5 | 2.20 | 24.1 | 243 | 93.3 |
| Water | 89.8 | 3.15 | 7.00 | 404 | ||||
| Entrainer | 5.80 | 3.71 | 90.5 | 553 | ||||
| Still liquid | 1.96 | 12.6 | 80.4 | 1.36 | 3.68 | 1456 | ||
| 4 | Charging | 7.71 | 11.7 | 62.2 | 2.25 | 16.1 | 1933 | 82.5 |
| Water | 84.6 | 8.00 | 7.37 | 140 | ||||
| Entrainer | 3.36 | 5.98 | 90.9 | 291 | ||||
| Still liquid | 1.38 | 15.1 | 80.1 | 1.00 | 2.42 | 1502 | ||
| 5 | Charging | 7.77 | 11.9 | 62.9 | 2.28 | 15.1 | 2780 | 85.3 |
| Water | 80.6 | 8.86 | 10.5 | 211 | ||||
| Entrainer | 3.55 | 4.70 | 91.9 | 417 | ||||
| Still liquid | 1.46 | 15.2 | 80.4 | 1.16 | 0.66 | 2152 | ||
| 6 | Charging | 7.93 | 12.1 | 61.8 | 2.34 | 15.7 | 1017 | 84.3 |
| Water | 90.3 | 9.27 | 10.9 | 79 | ||||
| Entrainer | 3.15 | 5.14 | 91.6 | 141 | ||||
| Still liquid | 1.60 | 15.4 | 79.0 | 1.16 | 2.84 | 797 | ||
| 7 | Charging | 7.21 | 11.0 | 58.3 | 2.12 | 21.3 | 1894 | 83.8 |
| Water | 86.1 | 8.10 | 5.85 | 119 | ||||
| Entrainer | 3.20 | 2.57 | 94.2 | 378 | ||||
| Still liquid | 1.58 | 15.0 | 79.1 | 1.47 | 2.85 | 1397 |
Table 2 light constituent, interim fraction component table (m/m, * 10
-2)
| Sequence number | Charging | Discharging | |||||||||
| Dehydration still liquid | Light constituent | Interim fraction | |||||||||
| Formic acid | Acetate | Water | Entrainer | Impurity | Weight (g) | Formic acid | Acetate | Other | Weight (g) | ||
| 1 | 17.0 | 77.1 | 1.81 | 2.99 | 1.10 | 585 | 39 | 41.4 | 50.0 | 8.60 | 202 |
| 2 | 12.6 | 80.4 | 1.96 | 3.68 | 1.36 | 1360 | 80 | 38.0 | 51.8 | 10.2 | 462 |
| 3 | 15.1 | 80.1 | 1.38 | 2.42 | 1.00 | 1454 | 87 | 43.6 | 52.3 | 4.10 | 422 |
| 4 | 15.2 | 80.4 | 1.46 | 0.66 | 1.16 | 2050 | 112 | 42.2 | 54.1 | 3.70 | 608 |
| 5 | 15.4 | 79.0 | 1.60 | 2.84 | 1.16 | 721 | 57 | 43.2 | 54.1 | 2.70 | 208 |
| 6 | 15.0 | 79.1 | 1.58 | 2.85 | 1.47 | 1135 | 83 | 41.2 | 51.2 | 7.60 | 340 |
The result shows: because of formic acid, acetate component concentration in the interim fraction have bigger variation, the formic acid component concentration improves, greater than 38%.The acetate component concentration reduces, and less than 45%, water and foreign matter content reduce, and this interim fraction is added to the next batch nitration mixture and handles together, when treating that formic acid content reaches 40-50% in the interim fraction, collects interim fraction, with its rectifying, fractionates out finished product formic acid and finished product acetate.Produce the 1140 tons of meters of acid that boil per year, interim fraction is about 364 tons.
Embodiment 3
After isolating light constituent and interim fraction on the knockout tower, tower top temperature 116.1-118.0 ℃, separated and collected gets the acetate finished product.Separate to such an extent that the purity and the yield of acetate finished product sees Table 3.
The purity of table 3 acetate finished product and yield (m/m, * 10
-2)
| Sequence number | Charging | Discharging | Acetic acid yield | |||||||||
| Dehydration still liquid | Finished product acetate | |||||||||||
| Formic acid | Acetate | Water | Entrainer | Impurity | Quality (g) | Formic acid | Acetate | Water | Impurity | Quality (g) | ||
| 1 | 17.0 | 77.1 | 1.81 | 2.99 | 1.10 | 585 | 0.01 | 99.1 | 0.73 | 0.16 | 344 | 75.4 |
| 2 | 12.6 | 80.4 | 1.96 | 3.68 | 1.36 | 136 0 | 0.25 | 99.2 | 0.53 | 0.02 | 818 | 74.2 |
| 3 | 15.1 | 80.1 | 1.38 | 2.42 | 1.00 | 145 4 | 0.18 | 99.0 | 0.59 | 0.23 | 945 | 80.3 |
| 4 | 15.2 | 80.4 | 1.46 | 0.66 | 1.16 | 205 0 | 0.17 | 99.4 | 0.38 | 0.05 | 133 0 | 80.2 |
| 5 | 15.4 | 79.0 | 1.60 | 2.84 | 1.16 | 721 | 0.00 | 99.6 | 0.32 | 0.08 | 456 | 79.7 |
| 6 | 15.0 | 79.1 | 1.58 | 2.85 | 1.47 | 113 5 | 0.17 | 99.5 | 0.31 | 0.03 | 712 | 78.9 |
The result shows: isolated finished product acetate, purity is greater than 99%, once through yield average out to 78.1%.
Embodiment 4
The azeotropic dehydration aqueous phase contains entrainer and impurity if directly discharging will increase the consumption of entrainer, and waste water is more difficult.Therefore, reclaim entrainer from aqueous phase behind this test azeotropic dehydration, recovery method utilizes dehydration tower rectifying, and distillate is separated into water and entrainer mutually in water trap, collect the entrainer phase, reclaims the entrainer data from aqueous phase behind the azeotropic dehydration and sees Table 4.
Table 4 dehydration water entrainer rate of recovery data sheet (m/m, * 10
-2)
| Charging | Discharging | The entrainer rate of recovery | ||||||
| The dehydration water | Water | Entrainer | ||||||
| Entrainer | CODcr (mg/ L) | Quality (g) | Entrainer | CODcr (mg/ L) | Quality (g) | Water | Quality (g) | |
| 8.20 | 9.78× 10 4 | 1150 | 0.68 | 8.82× 10 3 | 1061 | 3.00 | 89 | 91.5 |
The result shows: the dehydration water is through reclaiming entrainer, and the entrainer rate of recovery is 91.5%, and the entrainer in the discharging reduces to 0.68% by 8.20%, and the CODcr value is by 9.78 * 10
4Mg/l reduces to 8.82 * 10
3Mg/l, because quantity discharged is less, this strand waste water can directly enter Sewage treatment systems and handle.
Claims (1)
1. the separation method of a formic acid, acetate aqueous mixture is characterized in that it comprises the following steps:
(1) add the entrainer ethyl acetate in formic acid, acetate aqueous mixture, place rectifying tower water trap rectifying azeotropic dehydration, the content of residuary water is 1.38-1.99 weight % in the dehydration tower bottoms,
(2) the dehydration tower bottoms that is 1.38-1.99 weight % with the middle water content of step (1) places separating rectification tower to carry out rectifying, be divided into three cuts: light constituent, collecting tower top temperature is 97.0-101.8 ℃ of cut, interim fraction, collecting tower top temperature is 101.9-116.0 ℃ of cut, finished product acetate is collected 116.1-118.0 ℃ of cut of tower top temperature
(3) collect the middle isolated water of water trap of using of step (1),, reclaim entrainer again through rectifying,
(4) collect smart distilled light constituent and interim fraction in the step (2), repeat step (1) operation again in adding next batch formic acid, the acetate aqueous mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 01108268 CN1239457C (en) | 2001-02-28 | 2001-02-28 | Separation method for equatic mixture of formic acid and acetic acid |
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| CN 01108268 CN1239457C (en) | 2001-02-28 | 2001-02-28 | Separation method for equatic mixture of formic acid and acetic acid |
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| CN1239457C true CN1239457C (en) | 2006-02-01 |
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| CN101117309B (en) * | 2006-08-04 | 2010-07-28 | 中国石油天然气股份有限公司 | Dewatering device of methyl isobutyl ketone synthetic liquid |
| CN102225963A (en) * | 2011-05-13 | 2011-10-26 | 周逸明 | Method for reducing acetonitrile residue in polypeptide medicament |
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