CN1634842A - Method for refining acetic acid - Google Patents
Method for refining acetic acid Download PDFInfo
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- CN1634842A CN1634842A CN 200410067178 CN200410067178A CN1634842A CN 1634842 A CN1634842 A CN 1634842A CN 200410067178 CN200410067178 CN 200410067178 CN 200410067178 A CN200410067178 A CN 200410067178A CN 1634842 A CN1634842 A CN 1634842A
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- acetic acid
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Abstract
The invention relates to a method for refining high quality of acetic acid, characterized by filling acetic acid -insoluble solid strong oxidizer in adsorption column 1, acetic acid passing the oxidizer for removing the impurity in acetic acid, then acetic acid passing adsorption column 2 filled with alumina and adsorption column 3 filled with active carbon for refining acetic acid again to make the formic acid content in acetic acid be below 50ppm and reduce the content of iodine ion.
Description
One, technical field:
The present invention relates to a kind of process for purification of acetic acid, particularly disclose the process for purification of the acetic acid of producing by the low-pressure methanol oxo synthesis.
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 by product, as formic acid, propionic acid and halide-containing etc. further improve for making the acetate products quality, to satisfy the different demands of market to quality product, developed and originally removed trace impurity in the acetate products, as the process for purification of formic acid, halide-containing.Produce distillation and separation method Dichlorodiphenyl Acetate upward commonly used at present and make with extra care, but because the boiling point of formic acid near the acetic acid boiling spread, is difficult to make the content of formic acid to reduce with traditional rectificating method.
The method of formic acid has U.S. Patent No. 2,656 in the reduction acetic acid of now having known, 379 proposed under the temperature more than 260 ℃, the method for formic acid being decomposed by activated alumina; Russian patent No.57,862 propose with the method that heats up, and utilize other dehydrogenation catalyst that formic acid is decomposed.Aforesaid method all has a shortcoming, promptly in decompose formic acid, also can make a large amount of acetic acid obtain decomposing.Also have some patents, U.S. Patent No. 2,913,492; No.2,688,635; No.3,488,383 propose to use precious metals such as platinum, osmium, rhodium, iridium and lutetium as catalyzer, utilize redox system to remove the method for formic acid removal, but these method complicated operations and cost height.
U.S. Patent No. 4,061,546 have proposed to utilize the formic acid impurity in the hexavalent chromium compound removal acetic acid, the handled acetic acid of this method has fully been removed halogen impurities, but still contain a small amount of formic acid impurity (100ppm), and this invention fully contacts hexavalent chromium compound with the acetic acid that contains formic acid impurity, and the acetic acid after making with extra care reclaims by modes such as rectifying or ion-exchanges, the reduzate trivalent chromium then is oxidized to sexavalent chrome again by the form that adds strong acid and electrolytic oxidation, to recycle.The consumption of the required hexavalent chromium compound of oxidation formic acid such as is at least at chemical equivalent, preferential 2～3 times of chemical equivalents in this method.In a word, the acetic acid that this method is handled must fully be removed halogen impurities in advance, and hexavalent chromium compound is advisable with excessive use.Resulting trivalent chromium uses through strong acid and electrolytic oxidation cycle of treatment.The acetic acid that China's pending application has proposed to contain formic acid impurity and consumption doubly stoichiometric oxygenant such as are lower than and contact, used oxygenant is a potassiumchromate, form is the aqueous solution, further reclaim with the acetic acid after oxygenant contacts by rectifying, obtain formic acid content and be less than 50ppm, iodine impurity is less than the high-quality acetic acid of 2～10ppb.
Three, summary of the invention:
The present invention proposes and utilize solid oxidizing agent, as sodium bromate, potassium bromate, potassium aluminate, sodium aluminate, ammoniumper chlorate, potassium perchlorate, Textone etc., wherein be preferably potassium bromate, the method of refining acetic acid, this method is simple and easy to do, formic acid content in the acetic acid can be reduced to below the 50ppm effectively, in addition, can also effectively reduce the content of iodide ion impurity.
The present invention is achieved in that a kind of process for purification of acetic acid, 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 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, gac, the further Dichlorodiphenyl Acetate of aluminum oxide are made with extra care, and the formic acid foreign matter content in the acetic acid is reduced to below the 50ppm, and reduce the content of iodide ion impurity.
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 8～350 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 formic acid 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 for decolouring, further the Dichlorodiphenyl Acetate product is made with extra care.The hot water flow of being come out by heating thermostat 4 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 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 acetate products of level in the pure and mild carbon monoxide carbonylation reaction of catalyst system carapax et plastruw testudinis institute's industrialization continuous production or batch production.
Be used for oxidizing reaction adsorption column material select the character that will consider potassium bromate for use, material of the present invention is a glass.
The contact temperature can be chosen in 40～80 ℃ aptly, but from optimum handling effect and economic angle, optimum temps is chosen in 60 ℃.The contact temperature is by heating thermostat 4 controls.
With the visual response condition and deciding duration of contact of potassium bromate, the concentration that depends on impurity with contact factor such as temperature, determine that through the flow velocity of adsorption column the flow velocity of acetic acid can be chosen in 0.20～2ml/s aptly by acetic acid duration of contact.
Contact pressure there are not strict restriction, general preferred normal pressure.
The detection method of formic acid content adopts national standard method (the mensuration iodimetry,iodometry of formic acid content in the GB/T 1628.4-2000 industrial acetic) in the acetic acid.
Methyl-iodide adopts gas chromatography determination, and iodide ion adopts spectrophotometry.
Further specify the present invention below by embodiment and reference example.
Embodiment:
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 4, is the product that obtains by adsorption column 3 distilled acetic acid.
The acetate products that embodiment is obtained carries out product analysis.
The main quality index of product the results are shown in following table:
| Methyl-iodide (ppb) | ????6.915 |
| Propionic acid (ppm) | ????178 |
| Formic acid (ppm) | ????28.812 |
| Iodide ion (mg) | ????70.93 |
| Water (ppm) | ????1044 |
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 |
Claims (7)
1. the process for purification of an acetic acid, 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 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, gac, the further Dichlorodiphenyl Acetate of aluminum oxide are made with extra care, and the formic acid foreign matter content in the acetic acid is reduced to below the 50ppm, and reduce the content of iodide ion impurity.
2. the process for purification of acetic acid according to claim 1, it is characterized in that: the used solid strong oxidizer that is insoluble to acetic acid is a potassium bromate.
3. the process for purification of acetic acid according to claim 1 by the flow through air speed of potassium bromate of purified acetic acid is: 0.20～2ml/s.
4. the process for purification of acetic acid according to claim 1, the temperature when being contacted with potassium bromate by purified acetic acid is: 40～80 ℃.
5. the process for purification of acetic acid according to claim 1, it is characterized in that: processing pressure is a normal pressure.
6. the process for purification of acetic acid according to claim 1, it is characterized in that: the dimensions of used gac is 8～350 orders.
7. the process for purification of acetic acid according to claim 1, it is characterized in that: the diameter dimension of used alumina globule is 40 μ m～2mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410067178 CN1634842A (en) | 2004-10-15 | 2004-10-15 | Method for refining acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410067178 CN1634842A (en) | 2004-10-15 | 2004-10-15 | Method for refining acetic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1634842A true CN1634842A (en) | 2005-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410067178 Pending CN1634842A (en) | 2004-10-15 | 2004-10-15 | Method for refining acetic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445443B (en) * | 2008-12-17 | 2012-07-18 | 上海吴泾化工有限公司 | Production method of edible acetic acid |
| WO2014115826A1 (en) | 2013-01-25 | 2014-07-31 | 株式会社ダイセル | Method for manufacturing carboxylic acid |
| US10758838B2 (en) * | 2015-02-25 | 2020-09-01 | Sabic Global Technologies B.V. | Process for removing impurities from acetic acid |
-
2004
- 2004-10-15 CN CN 200410067178 patent/CN1634842A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445443B (en) * | 2008-12-17 | 2012-07-18 | 上海吴泾化工有限公司 | Production method of edible acetic acid |
| WO2014115826A1 (en) | 2013-01-25 | 2014-07-31 | 株式会社ダイセル | Method for manufacturing carboxylic acid |
| US10758838B2 (en) * | 2015-02-25 | 2020-09-01 | Sabic Global Technologies B.V. | Process for removing impurities from acetic acid |
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