CN1221511C - Acetic acid purification process - Google Patents
Acetic acid purification process Download PDFInfo
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- CN1221511C CN1221511C CN 03150852 CN03150852A CN1221511C CN 1221511 C CN1221511 C CN 1221511C CN 03150852 CN03150852 CN 03150852 CN 03150852 A CN03150852 A CN 03150852A CN 1221511 C CN1221511 C CN 1221511C
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- acetic acid
- oxygenant
- formic acid
- purification process
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Abstract
The present invention relates to a method for purifying acetic acid. The formic acid impurity content in acetic acid prepared in the carbonylation reaction is reduced to less than 100 ppm by the method, and simultaneously, the iodine impurities content can be obviously reduced. The method comprises the steps: firstly, the acetic acid containing formic acid impurities is in contact with an oxidizing agent; then, a rectification method is used for recovering the purified acetic acid. The method of the present invention preferably uses potassium chromate as the oxidizing agent.
Description
Technical field
The present invention relates to the purification process of acetic acid, more specifically relate to from acetic acid, remove the method for formic acid removal impurity.
Background technology
The liquid-phase carbonylation reaction of methyl alcohol is a kind of acetic acid production method of industrial extensive employing.Under this operating method, adopt rhodium or iridium usually as catalyzer, with halogen compounds such as methyl-iodide or hydrogen iodides as cocatalyst.Generally contain impurity such as formic acid, a small amount of cocatalyst, methyl acetate, propionic acid, acetaldehyde in the thick acetic acid that carbonylation reaction is produced.Distillation and separation method commonly used carries out purifying to thick acetic acid in the production.But because the boiling point of formic acid is difficult to remove effectively formic acid with traditional rectificating method near the acetic acid boiling spread.Contain the formic acid impurity that is no more than 500ppm in the general acetic acid finished product; And contain other impurity such as iodide, methyl acetate, propionic acid, acetaldehyde of trace.Continuous expansion along with acetate products market and acetic acid derived product scope, sometimes the formic acid content in the acetate products requires to be controlled at below the 100ppm, for example in the production requirement raw material acetic acid of product such as acetic anhydride, cellulose acetate the content of formic acid below 100ppm.
The method of formic acid is included under the temperature more than 260 ℃ in the disclosed reduction acetic acid, the method (U.S. Patent No. 2,656,379) of formic acid being decomposed by activated alumina.Russian patent No.57,862 have introduced with the method that heats up, and utilize other dehydrogenation catalyst that formic acid is decomposed.Aforesaid method also can make a large amount of acetic acid obtain decomposing in decompose formic acid.In addition some patent disclosures with precious metals such as platinum, osmium, rhodium, iridium, lutetium as catalyzer, utilize redox system to remove method (U.S. Patent No. 2,913,492 of formic acid; No.2,688,635; No.3,488,383).These methods are removed formic acid cost height and complicated operation.
U.S. Patent No. 4,061,546 have introduced the method for utilizing hexavalent chromium compound to handle the formic acid impurity in the acetic acid.The handled acetic acid of this method has been for fully having removed halogen impurities, but contains a small amount of formic acid impurity (surpassing 100ppm).This method fully contacts hexavalent chromium compound with the acetic acid that contains formic acid impurity, acetic acid behind the purifying 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, preferred 2-3 times of chemical equivalent 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.After handling, resulting trivalent chromium process strong acid and electrolytic oxidation recycle.
At present domestic about the formic acid content in the acetic acid being reduced to the treatment process below the 100ppm, do not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide the acetic acid purification process that a kind of technology is simple, cost is low, respond well.Thereby effectively the formic acid content in the resulting acetic acid of the carbonylation reaction mode of production is reduced to below the 100ppm.
The handled acetic acid of the inventive method refers to by the liquid-phase carbonylation reaction institute's industrialization continuous production of methyl alcohol or the acetate products of batch production.Contain impurity such as formic acid, iodide, acetaldehyde, ritalin, propionic acid in this product, wherein the content of formic acid is no more than 500ppm.The inventive method may further comprise the steps:
(1) acetic acid that contains formic acid impurity is contacted with oxygenant
(2) from step (1) product, reclaim purified acetic acid by rectifying
Oxygenant is a hexavalent chromium compound among the present invention, the chromic salt and the dichromate of preferred alkali metal containing, and as potassiumchromate, Sodium chromate, potassium bichromate, sodium dichromate 99 etc., wherein more preferably potassiumchromate, potassium bichromate most preferably are potassiumchromate.Can produce side reaction because of local heating is inhomogeneous owing to directly adding solid processing agent and generate the ketone reducing substance, so oxygenant is with the form use of the aqueous solution.Because the high rectifying recovering effect that can influence acetic acid of moisture content is brought moisture into when using oxygenant in order to reduce as far as possible in acetic acid, oxygenant should be best with the saturated aqueous solution.The present invention discovers that when utilizing sexavalent chrome that formic acid oxidation is become carbonic acid gas, its reduzate trivalent chromium can also reduce the iodine foreign matter content in the acetic acid effectively.When the iodine foreign matter content was no more than 1ppm in the acetic acid, the inventive method can be reduced to 2ppb-10ppb with iodine impurity when removing formic acid.In the inventive method, the consumption of oxygenant is decided on the content of formic acid impurity in the acetic acid, and as when formic acid content is the 300ppm left and right sides, the oxygenant consumption is at 0.67 times more than the equivalent, when formic acid content was the 200ppm left and right sides, the oxygenant consumption can be at 0.5 times more than the equivalent.From removing the angle of formic acid impurity, when use waits times equivalent or doubly normal oxygenant such as surpasses, more remarkable effect, but when the consumption of oxygenant reach etc. times equivalent or etc. times equivalent when above, can in the rectification-recovery process of acetic acid, cause oxidation corrosion to rectifying tower, excessive oxygenant also can be oxidized to the iodine in the acetic acid volatile iodine simultaneously, thereby causes the corrosion of iodine to rectifying tower, and influences the colourity of finished product acetic acid.Therefore the consumption of oxygenant is advisable a times chemical equivalent such as to be no more than, and is good times chemical equivalent such as to be lower than especially.
Contain the acetic acid of formic acid impurity and oxygenant the way of contact can for stir, reflux, altogether stream, adverse current, cross-stream, boil etc.The contact temperature is 16～400 ℃, preferred 100～180 ℃, contact pressure is not had strict restriction, but be lower than normal pressure, normal pressure or be higher than equal implementation step (1) under the condition of normal pressure, general preferred normal pressure.The concentration, the factor such as contact temperature etc. that depend on impurity and oxygenant duration of contact are generally several seconds to 30 minute, preferred 10 seconds-20 minutes.
Through the acetic acid of oxidizer treatment, to carry out rectifying by rectifying tower and reclaim, the number of effective plates of rectifying tower is controlled at 30～60 theoretical trays.The acetic acid of purifying is from the middle and lower part charging of rectifying tower, and the product acetic acid after the rectifying is by the rectifier discharging, and rectifying tower top pressure keeps pressure-fired, and temperature is controlled at 110～140 ℃.Waste liquid after the rectifying contains I
-, K
+, Cr
3+Plasma, from the rectifier bottoms discharging, column bottom temperature is 150～160 ℃.Waste liquid is through burning the residue landfill disposal.
The detection method of formic acid foreign matter 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.
Description of drawings
Fig. 1 is the process flow sheet of acetic acid purification process of the present invention
Beneficial effect
1, the acetic acid purification process of the present invention's proposition can reduce the content of formic acid impurity effectively, and oxidant is used Amount less, operating procedure is simple, and cost is low.
2, the acetic acid purification process of the present invention's proposition can show when effectively reducing the formic acid impurity content Work reduces the content of iodine impurity. Thereby the unnecessary halogen impurities of fully removing in advance before processing acetic acid, Simplified operating procedure.
Embodiment
Below in conjunction with process flow sheet and embodiment the inventive method is further elaborated, but does not limit the present invention:
With pressure-feed mode continuous aqueous solution (being advisable with saturated aqueous solution) that feeds oxygenant in suitable containers, this container should be able to bear certain pressure and not allow corrosion-vulnerable, can adopt materials such as stainless steel or lass lining.The bottom of container is connected with output tube (being provided with spinner-type flowmeter), discharge with the under meter controlled oxidation agent aqueous solution, the other end of output tube inserts in the acetic acid transfer lime, pending acetic acid flows with the turbulent form in transfer lime, can guarantee that like this oxygenant contacts with the acetic acid thorough mixing, the contact temperature is controlled by the temperature of acetic acid itself, the mixed reaction solution of acetic acid and oxygenant from rectifying tower on the lower side the position send into rectifying tower, by carry heat up in a steamer after, the acetic acid of purifying (formic acid content is lower than 100ppm) flows out from rectifier and reclaims, and contains I
-, K
+, Cr
3+Isoionic waste liquid goes out from tower bottom flow, removes by the mode of burning, burying then.
Employed material and equipment comprise among the following embodiment: 1000ml three neck round-bottomed flasks, three ecks of three-necked flask are respectively applied for the insertion thermometer, fractional column is installed and is added sample and oxygenant.The GS12-2 electronics constant speed stirrer that Shanghai Special Medical Appliances Factory produces, the TC-15 shell type thermostatted that Haining medical apparatus and instruments factory of Xinhua produces, 700/24 * 2 fractional column that strong glassware company limited produces is built in Shanghai, having dosed specification in the fractional column is external diameter 8mm, internal diameter 6mm, the hollow porcelain ring of high 10mm (available from reagent shop, Shanghai) makes this fractional column reach 3-5 column plate effect, and thermometer and condenser are installed on the fractional column.Oxygenant storage tank in the acetic acid production device, the heavy constituent rectifying tower.
The detection method of formic acid impurity is: GB/T 1628.4-2000 (the mensuration iodimetry,iodometry of formic acid content in the industrial acetic).
The detection method of iodine impurity is: methyl-iodide adopts gas chromatography determination, and iodide ion adopts spectrophotometry.The content summation of methyl-iodide and iodide ion is the iodine total amount.
The acetic acid of purified processing is taken from the thick acetic acid in the production equipment among the following embodiment 1-3, and the moisture content that detects in the acetic acid is that 860ppm, formic acid content are that 300ppm, iodine total amount are 60ppb.
The acetic acid of purified processing is taken from acetic acid factory laboratory among the embodiment 4-5, and the formic acid content in the acetic acid is 124ppm after testing.
Embodiment 1
Take by weighing the 58.2g potassiumchromate, be dissolved in the 100ml water, make concentration and be 36.79% potassium chromate solution.In the 1000ml three-necked flask, add 200g acetic acid, in three-necked flask, adds the 0.12ml potassium chromate solution, stir and extremely seethe with excitement, distill through 700/24 * 2 fractional column with the shell type oven heated with the electronics constant speed stirrer with transfer pipet.Get 118-140 ℃ of cut.By analysis: the formic acid content in the cut is 20ppm, and the iodine total amount is 2ppb.
Embodiment 2
Take by weighing the 7g potassium bichromate, be dissolved in the 100ml water, make concentration and be 6.5% potassium bichromate solution.In the 1000ml three-necked flask, add 200g acetic acid, in three-necked flask, adds the 1ml potassium bichromate solution, stir and extremely seethe with excitement, distill through 700/24 * 2 fractional column with the shell type oven heated with the electronics constant speed stirrer with transfer pipet.Get 118-140 ℃ of cut.By analysis: the formic acid content in the cut in the cut is 10ppm, and the iodine total amount is 4ppb.
Embodiment 3
The oxygenant groove is set in the acetic acid testing apparatus, in the oxygenant groove, adds 36.79% potassium chromate solution, the acetic acid throughput be controlled at the 7-8 ton/hour, the oxygenant add-on was controlled at 5-6kg/ hour.Recovery is from the effusive acetate products in rectifying column top.Formic acid content in the product is 25ppm by analysis, and the iodine total amount is 6.5ppb.
Embodiment 4
Take by weighing the 58.2g potassiumchromate, be dissolved in the 100ml water, make concentration and be 36.79% potassium chromate solution.In the 1000ml three-necked flask, add 100g acetic acid, in three-necked flask, adds 26 μ l potassium chromate solutions, stir and extremely seethe with excitement, distill through 700/24 * 2 fractional column with the shell type oven heated with the electronics constant speed stirrer with microsyringe.Get 118-140 ℃ of cut.By analysis: the formic acid content in the cut is 60ppm.
Embodiment 5
Take by weighing the 58.2g potassiumchromate, be dissolved in the 100ml water, make concentration and be 36.79% potassium chromate solution.In the 1000ml three-necked flask, add 100g acetic acid, in three-necked flask, adds 19 μ l potassium chromate solutions, stir and extremely seethe with excitement, distill through 700/24 * 2 fractional column with the shell type oven heated with the electronics constant speed stirrer with microsyringe.Get 118-140 ℃ of cut.By analysis: the formic acid content in the cut is 70ppm.
Claims (5)
1. the purification process of an acetic acid, this method is reduced to the formic acid foreign matter content below the 100ppm, simultaneously the iodine foreign matter content is reduced to 2-10ppb, the acetic acid of indication makes by the liquid-phase carbonylation reaction of methyl alcohol, contain the iodine impurity that is no more than 1ppm in this acetic acid, the method is characterized in that may further comprise the steps:
(1) acetic acid that contains formic acid impurity and consumption doubly stoichiometric oxygenant such as are lower than and contact, and wherein said oxygenant is a hexavalent chromium compound, and the type of service of oxygenant is the aqueous solution;
(2) from step (1) product, reclaim purified acetic acid by rectifying.
2. the purification process of acetic acid according to claim 1, the type of service that it is characterized in that described oxygenant is a saturated aqueous solution.
3. the purification process of acetic acid according to claim 1 is characterized in that described oxygenant is the chromic salt or the dichromate of alkali metal containing.
4. the purification process of acetic acid according to claim 3 is characterized in that described oxygenant is potassiumchromate or potassium bichromate.
5. the purification process of acetic acid according to claim 4 is characterized in that described oxygenant is a potassiumchromate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150852 CN1221511C (en) | 2003-09-05 | 2003-09-05 | Acetic acid purification process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150852 CN1221511C (en) | 2003-09-05 | 2003-09-05 | Acetic acid purification process |
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| Publication Number | Publication Date |
|---|---|
| CN1523001A CN1523001A (en) | 2004-08-25 |
| CN1221511C true CN1221511C (en) | 2005-10-05 |
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|---|---|---|---|
| CN 03150852 Expired - Lifetime CN1221511C (en) | 2003-09-05 | 2003-09-05 | Acetic acid purification process |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312101C (en) * | 2004-10-15 | 2007-04-25 | 上海吴泾化工有限公司 | Acetic acid refining method for improving acetic acid potassium permanganate test time |
| CN100450988C (en) * | 2006-06-19 | 2009-01-14 | 上海吴泾化工有限公司 | Low pressure device for synthesizing acetic acid by methanol carbonylation |
| CN102070434B (en) * | 2010-12-31 | 2013-07-17 | 河南省华鼎高分子合成树脂有限公司 | Treatment method for waste liquid produced during production of maleimide compound |
| CN102746137B (en) * | 2012-08-03 | 2014-10-22 | 天津长芦海晶集团有限公司 | Method for producing medical glacial acetic acids by using industrial glacial acetic acids |
| 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 |
-
2003
- 2003-09-05 CN CN 03150852 patent/CN1221511C/en not_active Expired - Lifetime
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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: 20150120 |
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Effective date of registration: 20150120 Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: SHANGHAI HUAYI ENERGY CHEMICAL CO.,LTD. Address before: 200241 No. 4600 Wu Long Road, Shanghai Patentee before: Shanghai Wujing Chemical Co.,Ltd. |
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Granted publication date: 20051005 |
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