CN1312101C - Acetic acid refining method for improving acetic acid potassium permanganate test time - Google Patents
Acetic acid refining method for improving acetic acid potassium permanganate test time Download PDFInfo
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- CN1312101C CN1312101C CNB2004100671799A CN200410067179A CN1312101C CN 1312101 C CN1312101 C CN 1312101C CN B2004100671799 A CNB2004100671799 A CN B2004100671799A CN 200410067179 A CN200410067179 A CN 200410067179A CN 1312101 C CN1312101 C CN 1312101C
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- acetic acid
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Abstract
The present invention relates to a method for removing reducing impurities from acetic acid and enhancing the potassium permanganate test time of the acetic acid. The method is characterized in that a solid strong oxidizer which is not dissolved in acetic acid is put in an adsorption column 1; the acetic acid flows through the oxidant, and the reducing impurities in the acetic acid are removed; then, the acetic acid flows through an adsorption column 2 loaded with alumina and an adsorption column 3 loaded with active carbon; and the water and the saturation aldehydes in the acetic acid are further removed, and then, the acetic acid is refined. The refined acetic acid is sampled to carry out potassium permanganate test; if the acetic acid still has many impurities, the refining process is repeated. The high-quality acetic acid with good potassium permanganate test time is prepared.
Description
One, technical field:
The present invention relates to a kind of process for purification of acetic acid, particularly disclose a kind of acetic acid process for purification that improves acetic acid potassium permanganate test period by the acetic acid of low-pressure methanol oxo synthesis production.
Two, background technology:
Acetic acid is as a kind of important industrial raw material, status in organic chemistry industry is very important, be widely used in fiber, softening agent, make lacquer, tackiness agent, copolymer resins and pharmacy, dyestuff, food, metal processing and Fine Organic Chemical product multiple industrial circle such as synthesize, be to develop a kind of faster important organic chemical industry's product in recent years in the world.
The method of producing acetic acid at present in the world has acetaldehyde oxidation, butane and lightweight oil oxidation style and methanol carbonylation.Wherein best method is exactly a methanol carbonylation, and this method is the productivity height of acetic acid not only, and the generation of by-product impurities has also reduced.Therefore when adopting this method to make acetic acid, can obtain the purity higher acetic acid of purity than the acetic acid made from other method.At present adopt the acetic acid total amount of low pressure carbonylation method production to account for more than 64% of world's acetic acid ultimate production in the world.
But, even adopt the low pressure carbonylation method, still can produce trace impurity, as reduzate as by product, formic acid, carbonyl compound and halide-containing, therefore when adopting method for preparing acetic acid, the long time is carried out in operate continuously, when the productive rate of acetic acid improves, the content of the impurity outside removing carbon dioxide and the propionic acid might increase, and impurity can pollute target product acetic acid, thereby makes the downgrade of acetate products.
At present, the method that the quality test of Dichlorodiphenyl Acetate is adopted is potassium permanganate reducing substance test (potassium permanganate test period), this method is for use in testing for the content of the trace reduction impurity that exists in the acetic acid, this quality test makes us to detect the small increase of trace impurity content, is difficult to even the detection of these trace impurities adopts the modern high performance instrument to analyze also.This test confirms that the quality of acetic acid is owing to this class reduction impurity reduces.This class impurity comprises aldehyde, especially unsaturated aldehyde.These aldehyde comprise multiple compound, they separately separation and to remove be very difficult, especially crotonaldehyde, 2-ethyl crotonaldehyde and analogue thereof (they are the enriched materials after the dehydration of acetaldehyde molecule) have the boiling point close with acetic acid, therefore, be difficult to by distillation this class trace impurity and acetic acid separated.
The method of now having known of removing these impurity is used the facture of ozone, peracetic acid and hydrogen in addition except distillation method (energy consumption is too big).
Japan pending application JP-A02-231448 has proposed to use the treatment process of hydrogen, under the situation that 0.01-10% (weight) hydrogenation catalyst exists, be about 17-200 ℃ and hydrogen pressure in temperature and be about under 1-30 the atmospheric condition, handle impure aceticanhydride with hydrogen.
Japan publication JP-B48-30615 has proposed to use the method for peracetic acid, this method is to add peracetic acid in acetic acid, make in the potassium permanganate test to show the short residence time, then resulting mixture is carried out distillation purifying, obtained the acetic acid of quality improvement.
Japan pending application JP-A61-56151 also discloses the method for making of the acetic acid of quality improvement, promptly adding peracetic acid in sour makes it show the short residence time in the potassium permanganate test, in temperature is that 50-120 ℃ scope internal heating is handled resulting mixture, makes the mixture of handling carry out distillation purifying.
Just be to use the ozone Dichlorodiphenyl Acetate to carry out the method for purifying in addition, relevant patent has (1) Japanese pending application JP-A60-222439, and this patent has proposed with gas processing aceticanhydride crude product ozoniferous.(2) Japanese publication JP-B61-2052 has proposed under the situation that does not have any catalyst metal compositions to use gas processing purity ozoniferous to be not less than 99% acetate products.(3) the Japanese pending application JP-A01-211548 corresponding to U.S. Pat 137844 proposes to contain the acetic acid that impurity is halogenide, unsaturated compound and carbonyl compound, under catalyzer existence or non-existent situation, contact with the ozone of capacity, with oxidation impurity recited above, reclaim the acetic acid of purifying.(4) Japanese Patent finds that concrete unsaturated compound is vinyl acetate and methyl crotonate in acetate products.Wherein, when acetic acid and acid anhydrides were produced simultaneously by ritalin and methyl alcohol or dme and methyl alcohol and reaction of carbon monoxide, methyl crotonate existed especially in a large number, and its boiling point and acetic acid are basic identical, therefore are difficult to remove with the distillation method of routine.So developing a kind of purifying, this invention contains vinyl acetate and methyl crotonate method as the acetic acid and/or the acid anhydrides of impurity, promptly combine by ozonize and fractionation by distillation, now acetic acid and/or the aceticanhydride with impure methyl crotonate and/or vinyl acetate contacts with ozone, ozone is excessive with respect to the mole number of the carbon-to-carbon double bond in the impurity, and the impurity that ozonize produces is removed by distillation again.Contain in a large number with ozonize after as the acetic acid of the unsaturated compound of impurity and/or aceticanhydride again generation as a large amount of impurity of aldehydes.To the acetic acid and/or the aceticanhydride distillation of ozonize, just can remove the unsaturated compound methyl crotonate and the vinyl acetate that are difficult to remove with conventional partition method again, thereby obtain good high-quality acetic acid of the residence time and/or aceticanhydride in the potassium permanganate test.(5) Japanese Patent is also developed the method for preparing high-purity acetic acid, be included in the reactor the aqueous solution of methyl alcohol and/or methyl acetate and the step of carbon monoxide successive reaction, from this reactor, extract the step of reacting fluid continuously out and in vaporizer, thereby the reacting fluid that is extracted is evaporated the step that obtains to contain the gas phase composition of acetic acid and this gas phase composition distillation is extracted simultaneously the cat head effluent in distillation tower from the cat head of this distillation tower, it is characterized in that with this overhead product of ozonize.In these treatment processs, estimate from angle economic and safety, use ozone or contain the method for ozone gas more favourable than other method, and in producing acetic acid and acid anhydrides just in practice.But have some shortcomings when handling with ozone: (1) can only handle saturated compound with ozone, and saturated aldehydes can not decompose by handling with ozone; (2) be saturated aldehydes by the degradation production that produces with the ozonize unsaturated compound, they still have reducing power, and therefore, they are the compounds that become more inferior, have still shortened the potassium permanganate test period.
Three, summary of the invention:
The present invention proposes the acetic acid process for purification that improves acetic acid potassium permanganate test period, the present invention utilizes the method for the refining acetic acid of oxygenant bromic acid potassium, this method is simple and easy to do, advantage with ozonize method above-mentioned, acetic acid can be refined to higher degree, make the time of potassium permanganate test acetic acid variable color obtain prolonging.
The present invention is achieved in that a kind of acetic acid process for purification that improves acetic acid potassium permanganate test period, it is characterized in that: pack in the adsorption column 1 with the solid strong oxidizer that is insoluble to acetic acid, the acetic acid oxygenant of flowing through, remove the reducing impurity in the acetic acid, acetic acid is flowed through alumina adsorption post 2 and the adsorption column 3 that gac is housed is housed then, further remove moisture and saturated aldehydes in the acetic acid, Dichlorodiphenyl Acetate is made with extra care, the potassium permanganate test is carried out in sampling in purified acetic acid, if more than the impurity, repeat above-mentioned treating process in the acetic acid.
In the method for the invention, suitable solid strong oxidizer is selected from sodium bromate, potassium bromate, potassium aluminate, sodium aluminate, ammoniumper chlorate, potassium perchlorate, Textone, wherein potassium bromate preferably.
Reducing impurity in the acetic acid comprises aldehyde, unsaturated aldehyde especially, and these aldehyde comprise multiple compound, crotonaldehyde especially, 2-ethyl crotonaldehyde and analogue thereof.
Further describe the present invention below in conjunction with accompanying drawing.
Four, description of drawings:
Accompanying drawing is an acetate products rectification flow sketch of the present invention.
Five, embodiment:
The present invention is raw materials used to be commercially available potassium bromate, gac and alumina globule, and the specification of gac is 70～200 orders, and the diameter of alumina globule is 40 μ m～2mm.
With reference to the accompanying drawings, oxygenant bromic acid potassium is housed in the adsorption column 1, is used for removing the reducing impurity of acetate products; The aluminium sesquioxide bead is housed in the adsorption column 2, is used to remove moisture; In the adsorption column 3 gac is housed, is used to remove saturated aldehydes, further the Dichlorodiphenyl Acetate product is made with extra care.The hot water flow of being come out by heating thermostat is through the shell side of three adsorption columns, acetic acid by adsorption column is heated, acetate products is squeezed into adsorption column 1 by pump, carry out contacting of for some time with potassium bromate, after removing reducing impurity, enter adsorption column 2 then, remove moisture, enter adsorption column 3 at last, the acetic acid that is come out by adsorption column 3 is resulting the finished product.
The present invention is applicable to the acetic acid of any rank (purity), and purification process of the present invention is preferably used in any other acetic acid of level of producing at the pure and mild carbon monoxide carbonylation of catalyst system carapax et plastruw testudinis.
Be used for oxidizing reaction the adsorption column material select the character that will consider potassium bromate for use, material of the present invention is a glass.
Temperature of reaction can be chosen in 50～80 ℃ aptly, and reaction temperature is spent low, and oxidation effectiveness is not good, and oxidation effectiveness improves along with the rising of temperature, but from economic angle, does not need to take so high temperature of reaction, and optimum temps is chosen in 60 ℃.Temperature of reaction is by heating thermostat 4 controls.Reaction pressure is a normal pressure.
Visual response condition and deciding duration of contact with potassium bromate.This oxidizing reaction does not adopt any catalyzer, and the effect of the reducing impurity reaction in potassium bromate and the acetic acid is fine, and determine that through the flow velocity of adsorption column the flow velocity of acetic acid can be chosen in 0.20～0.76ml/s aptly by acetic acid duration of contact.
The potassium permanganate test is: the water that adds 6 milliliters in the acetic acid in 20 milliliters, be added dropwise to the potassium permanganate solution of 3 milliliters 0.02mol/l then, oscillation mixture, measure solution and become the amber required time of standard from purple, required time of above-mentioned variable color is corresponding to the content of impurity in the sample, foreign matter content is higher, and the variable color required time is shorter.
Further specify the present invention below by embodiment and reference example.
The flow process for the treatment of process as shown in drawings, product acetic acid is squeezed into the adsorption column 1 that the 108g potassium bromate is housed by peristaltic pump, control speed is at 0.24ml/s, acetic acid is from lower to upper by adsorption column 1, enter the adsorption column 2 that the 100.51g gac is housed then, enter the adsorption column 3 that the 16g gac is housed at last, temperature is controlled at 60 ℃ by heating thermostat, is the product that obtains by adsorption column 3 distilled acetic acid.
The acetate products that embodiment 1 is obtained carries out the potassium permanganate test, gets the water of 6ml and the acetic acid of 20ml and adds test tube, is added dropwise to the potassium permanganate liquid of 3ml again, fully leaves standstill after the vibration, observes its variable color time.
The acetate products that embodiment 1 is obtained carries out product analysis.
The main quality index of product the results are shown in following table:
| Methyl-iodide (ppb) | 6.796 |
| Propionic acid (ppm) | 178 |
| Formic acid (ppm) | 62 |
| Iodide ion (mg) | 70.93 |
| Water (ppm) | 1044 |
| Potassium permanganate test period (min) | 210 |
Comparative Examples
Do not see the following form through the main quality index of purified acetate products:
| Methyl-iodide (ppb) | 15.358 |
| Propionic acid (ppm) | 165 |
| Formic acid (ppm) | 122 |
| Iodide ion (mg) | 69.51 |
| Water (ppm) | 937.7 |
| Potassium permanganate test period (min) | 3 |
Claims (10)
1. acetic acid process for purification that improves acetic acid potassium permanganate test period, it is characterized in that: pack in the adsorption column (1) with the solid strong oxidizer that is insoluble to acetic acid, the acetic acid oxygenant of flowing through, remove the reducing impurity in the acetic acid, the acetic acid adsorption column (3) of flowing through and alumina adsorption post (2) being housed and gac is housed then, further remove moisture and saturated aldehydes in the acetic acid, Dichlorodiphenyl Acetate is made with extra care, the potassium permanganate test is carried out in sampling in purified acetic acid, if more than the impurity, repeat above-mentioned treating process in the acetic acid.
2. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 1 is characterized in that: the used solid strong oxidizer that is insoluble to acetic acid is selected a kind of at sodium bromate, potassium bromate, potassium aluminate, sodium aluminate, ammoniumper chlorate, potassium perchlorate, Textone.
3. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 2, it is characterized in that: wherein the solid strong oxidizer is a potassium bromate.
4. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 1, it is characterized in that: the reducing impurity in the acetic acid is a unsaturated aldehyde.
5. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 4, it is characterized in that: unsaturated aldehyde is a crotonaldehyde, 2-ethyl crotonaldehyde.
6. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 2 is characterized in that: by the flow through air speed of potassium bromate of purified acetic acid be: 0.20～0.76ml/s.
7. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 2, it is characterized in that: the temperature when being contacted with potassium bromate by purified acetic acid is: 50～80 ℃.
8. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 1 is characterized in that: processing pressure is a normal pressure.
9. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 1, it is characterized in that: the dimensions of used gac is: 70～200 orders.
10. the acetic acid process for purification of raising acetic acid potassium permanganate test period according to claim 1, it is characterized in that: the diameter dimension of used alumina globule is: 40 μ m～2mm.
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| CNB2004100671799A CN1312101C (en) | 2004-10-15 | 2004-10-15 | Acetic acid refining method for improving acetic acid potassium permanganate test time |
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| CNB2004100671799A CN1312101C (en) | 2004-10-15 | 2004-10-15 | Acetic acid refining method for improving acetic acid potassium permanganate test time |
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| CN1312101C true CN1312101C (en) | 2007-04-25 |
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| AR094541A1 (en) | 2013-01-25 | 2015-08-12 | Daicel Corp | PROCEDURE TO PRODUCE CARBOXYL ACID |
| KR102281510B1 (en) * | 2017-03-22 | 2021-07-26 | 주식회사 다이셀 | Method for preparing acetic acid |
| CN112919678B (en) * | 2021-01-29 | 2023-04-18 | 江苏集萃托普索清洁能源研发有限公司 | Acetic acid production wastewater treatment process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434842A (en) * | 2000-02-24 | 2003-08-06 | 陶氏环球技术公司 | Improved flow carbonate polymer blends |
| US6667418B2 (en) * | 2002-04-16 | 2003-12-23 | Celanese International Corporation | Oxidation treatment of a recycle stream in production of acetic acid by methanol carbonylation |
| CN1523001A (en) * | 2003-09-05 | 2004-08-25 | 上海吴泾化工有限公司 | Acetic acid purification process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434842A (en) * | 2000-02-24 | 2003-08-06 | 陶氏环球技术公司 | Improved flow carbonate polymer blends |
| US6667418B2 (en) * | 2002-04-16 | 2003-12-23 | Celanese International Corporation | Oxidation treatment of a recycle stream in production of acetic acid by methanol carbonylation |
| CN1523001A (en) * | 2003-09-05 | 2004-08-25 | 上海吴泾化工有限公司 | Acetic acid purification process |
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Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER OWNER: WUJING CHEMICAL CO., LTD., SHANGHAI Effective date: 20150119 |
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Effective date of registration: 20150119 Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 200241 No. 4600 Wu Long Road, Shanghai Patentee before: Wujing Chemical Co., Ltd., Shanghai |