CN104045548A - Method for removal of trace iodine ions from acetic acid - Google Patents
Method for removal of trace iodine ions from acetic acid Download PDFInfo
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- CN104045548A CN104045548A CN201310081612.3A CN201310081612A CN104045548A CN 104045548 A CN104045548 A CN 104045548A CN 201310081612 A CN201310081612 A CN 201310081612A CN 104045548 A CN104045548 A CN 104045548A
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- acetic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for removal of trace iodine ions from acetic acid. Specifically, in a rectification process of preparing acetic acid by a methanol carbonylation synthesis technique, a nitrate or acetate solution of silver, palladium or mercury is added as an iodine removal reagent to remove the iodine ions in acetic acid to a content of less than 1ppb. The nitrate or acetate solution can be a water solution or an acetic acid solution thereof. The method involved in the invention is a single-tower iodine removal method. With no need for adding new equipment to the original acetic acid preparation process, the method can effectively remove iodine ions, and also does not affect separation of acetic acid and heavy components in the original process. In addition, the reaction generated iodide of silver, palladium or mercury is discharged from the tower bottom, and can be used for iodine removal repeatedly after regeneration treatment.
Description
Technical field
The present invention relates to a kind of method that removes Trace Iodine in acetic acid, specifically in the rectifying of the synthetic legal system acetic acid of methanol carbonyl, remove Trace Iodine, make the method for high purity acetic acid.
Background technology
Acetic acid is a kind of important basic organic chemical industry raw material, is widely used in the industries such as chemical industry, agricultural chemicals, medicine, national defence, electronics.Methanol carbonyl synthesis method is to prepare most popular method in process of acetic acid.Monsanto company has developed rhodium series catalysts low pressure carbonylation production technique in 20 century 70s, and methyl iodide is as auxiliary agent.British Petroleum Company p.l.c. (BP) and Celanese company are optimized this technique in succession, have developed respectively Cativa technique using metal iridium as Primary Catalysts and the AO Plus technique of low water content, and acetic acid production capacity is increased substantially.Although the Primary Catalysts difference of two kinds of techniques, all can be used methyl iodide to make auxiliary agent simultaneously, especially in AO Plus technique, use especially the lithium iodide of high density.Therefore in acetate products, inevitably contain iodine impurity.And when using acetic acid as raw material production derived product, iodide often cause many poisoning of catalyst inactivations.When with acetic acid and ethene synthesizing vinyl acetate, palladium, Au catalyst used are just very responsive to iodide.Therefore must find a kind of economically viable method to remove the iodine impurity in acetic acid.
Iodine impurity comprises organic iodine and the iodide ion taking methyl iodide as representative conventionally.Methyl iodide and acetic acid boiling point differ larger, therefore in follow-up separating technology, be easy to be removed by rectifying, but removing of iodide ion are comparatively difficult.Use traditional rectificating method the content of iodine impurity can only be controlled to ppm level.Therefore two-tower rectification method has been invented in patent US3772156 by Monsanto company, in rectifying, add the aqueous solution and the Hypophosporous Acid, 50 of Potassium ethanoate or potassium hydroxide, make it to react and removed with the iodide ion in acetic acid, make the acetate products of iodide ion content in ppb level through rectifying.Owing to using two-tower rectification, therefore the method energy consumption is higher.
The another kind of method of acetic acid refining is absorption method, makes acetic acid containing the micro iodine impurity deiodination adsorbent of flowing through, thereby makes highly purified acetic acid.Sorbent material has ion exchange resin, molecular sieve, macromolecule carbon bead etc., and these materials are processed the metals such as silver on back loading, mercury, palladium through different condition, can be used for removing the iodine impurity in acetic acid.The problem that the method exists is that cost is high, need to set up separately a set of de-iodine adsorption unit, and may respectively need to increase the adsorption bed of a non-year silver in the front and back of year silver-colored adsorption bed, the metal ion that is respectively used to remove in acetic acid carries the work-ing life of silver-colored sorbent material and adsorbs the silver ions being gone out by acetic acid drop to prevent from polluting acetic acid to extend.In addition, owing to being subject to the restriction of the factors such as silver carrying amount, carrying silver-colored sorbent material has certain loading capacity, therefore requires the iodine content in raw material acetic acid more low better.
Summary of the invention
In order to overcome the problems such as high, the complex process of consuming energy in the existing technique that removes iodide ion, de-iodine finite capacity, the invention provides a kind of method that removes Trace Iodine in acetic acid, specifically in the rectifying of the synthetic legal system acetic acid of methanol carbonyl, add the nitrate of silver, palladium or mercury or acetate solution as de-iodine reagent, iodide ion content in acetic acid is removed to below 1ppb, and this nitrate or acetate solution can be its aqueous solution or its acetum.In heavies column in acetic acid synthesized existing installation, silver, palladium or mercury ion react with iodide ion afterwards and other heavy constituent is discharged at the bottom of tower, obtain highly purified acetate products.
Method of the present invention is the de-iodine method of single tower, and the method need to not increase new device in the technique of original acetic acid processed, can either efficiently remove iodide ion, does not affect again separating of acetic acid and heavy constituent in original technique.The method is not subject to the impact of iodide ion content in charging acetic acid, can be used for removing from ppb level to ppm level iodide ion.In addition, reaction generate and from the iodide of silver, palladium or mercury of discharging at the bottom of tower after manipulation of regeneration, can be recycled and reused for de-iodine.
Compared with the alkaline metal iodide generating in prior art, the iodide of silver, palladium or the mercury generating in the present invention belong to insoluble compound, and solubleness is extremely low, and its solubility product is respectively 8.3 × 10
-17, 7.1 × 10
-9with 2.9 × 10
-29.Therefore in rectifying tower, silver, palladium or mercury more easily capture the iodide ion of trace, generate insolubles, and no longer discharge iodide ion with after it reacts.Thereby remove in the process of iodide ion in the present invention, only need to add silver, palladium or the mercury ion a little more than iodide ion stoichiometric ratio, can reach the object of deep removal iodide ion.And in prior art, use alkali metal hydroxide, and must add greatly excessive alkalimetal ion, iodide ion could be removed completely.
Preferably described in the present invention, nitrate or the acetate of silver, palladium or mercury are 2～10 with the ratio of the amount of substance of iodide ion.The nitrate of preferred described silver, palladium or mercury or acetate strength of solution are 0.1～10wt%.Preferably described de-iodine reagent is Silver Nitrate or Silver monoacetate solution.
In the present invention, the condition such as stage number, feeding rate, discharging speed, reflux ratio depends on separating of acetic acid and propionic acid, and present method does not strictly limit the operational condition of rectifying tower.But the preferably stage number > 40 of rectifying tower, and described de-iodine reagent from rectifying tower from tower at the bottom of 20～35 blocks of column plates position introduce distillation tower.Preferably the position of described pipeline 4 is to be less than 10 blocks of column plates apart from tower top; Rectifying tower service temperature is higher than 100 DEG C.
Brief description of the drawings
Fig. 1 is distillation tower and the conduit line map thereof of the synthetic legal system acetic acid of methanol carbonyl in the present invention;
Embodiment
Below by embodiment, the present invention is further elaborated, but is not limited in the embodiment enumerating.
Embodiment 1～5
Fig. 1 is the heavies column in the synthetic acetic acid technical process processed of methanol carbonyl, and this tower is for separating of acetic acid, propionic acid and other micro-high-boiling-point impurity.Through a series of rectification process before this tower, enter in the acetic acid of this tower and for example contain 0.1% propionic acid, 0.1% water, the content of iodide ion depends on whole carbonylic synthesis technology and generally between 100ppb～10ppm.The acetum that contains impurity enters in rectifying tower through pipeline 1, and de-iodine reagent solution of the present invention can join in pipeline 1 by pipeline 2, together enters rectifying tower, or join in rectifying tower through pipeline 3 with acetum.In the position that approaches tower top, through pipeline 4 side line extraction acetate products, the heavy constituents such as propionic acid and iodide are discharged at the bottom of tower through pipeline 5; Overhead product is the acetic acid containing a small amount of water, turns back in rectifying tower through cooling rear section, and all the other enter in lights column and recycle after pipeline 6 is discharged.
It is in 65 rectifying tower that the acetum that is 1ppm containing iodide ion is passed into stage number, passes into position for 25 blocks of column plates at the bottom of tower.The service temperature of rectifying tower is 118～120 DEG C, and pressure is a little more than normal atmosphere.Preparation, containing the acetum of 0.2wt% Silver monoacetate, joins in acetic acid by the molar ratio of metal ion shown in table 1 and iodide ion, then together enters in rectifying tower with acetic acid.From apart from 5 column plate side line extraction acetate products of tower top.Table 1 has been listed the iodide ion content in acetate products; The content of iodide ion ICP methods analyst.
Embodiment 6～8
Except using the silver nitrate aqueous solution of 1wt% as de-iodine reagent, other conditions are with embodiment 1, and analytical results is listed in table 1.
Embodiment 9
Except using the palladium nitrate aqueous solution of 1wt% as de-iodine reagent, other conditions are with embodiment 1, and analytical results is listed in table 1.
Table 1
Comparative example 1
Use the 25wt%KOH aqueous solution as de-iodine reagent solution, the mol ratio of KOH and iodide ion is 50, and other conditions are with embodiment 1, and analytical results is listed in table 1.
Above embodiment shows, uses acetate or the nitrate solution of silver, palladium or mercury in single rectifying tower, can effective elimination iodide ion, and in gained acetate products, iodide ion content, all lower than 1ppb, meets the requirement of industrial Dichlorodiphenyl Acetate quality product.The explanation of comparing with comparative example, the de-iodine effect of such de-iodine reagent is better than alkali metal hydroxide far away.
Claims (5)
1. one kind removes the method for Trace Iodine in acetic acid, it is characterized in that, in the rectifying of the synthetic legal system acetic acid of methanol carbonyl, add the nitrate of silver, palladium or mercury or acetate solution as de-iodine reagent, iodide ion content in acetic acid is removed to below 1ppb, and this nitrate or acetate solution can be its aqueous solution or its acetum.
2. method according to claim 1, is characterized in that, the nitrate of described silver, palladium or mercury or acetate are 2～10 with the ratio of the amount of substance of iodide ion.
3. method according to claim 1, is characterized in that, the nitrate of described silver, palladium or mercury or acetate strength of solution are 0.1～10wt%.
4. according to the method described in any one in claim 1～3, it is characterized in that, the stage number > 40 of rectifying tower, and described de-iodine reagent from rectifying tower from tower at the bottom of 20～35 blocks of column plates position introduce distillation tower.
5. according to the method described in any one in claim 1～3, it is characterized in that, described de-iodine reagent is Silver Nitrate or Silver monoacetate solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310081612.3A CN104045548B (en) | 2013-03-14 | 2013-03-14 | A kind of remove the method for Trace Iodine in acetic acid |
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|---|---|---|---|
| CN201310081612.3A CN104045548B (en) | 2013-03-14 | 2013-03-14 | A kind of remove the method for Trace Iodine in acetic acid |
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| CN104045548A true CN104045548A (en) | 2014-09-17 |
| CN104045548B CN104045548B (en) | 2016-08-10 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772156A (en) * | 1971-11-19 | 1973-11-13 | Monsanto Co | Purification of acetic acid streams by distillation |
| CN1041357A (en) * | 1988-09-27 | 1990-04-18 | Bp化学有限公司 | The removing method of iodine or iodide impurities |
| CN101811023A (en) * | 2010-03-11 | 2010-08-25 | 上海复旭分子筛有限公司 | Preparation method, product and applications thereof of acetate deep deiodination adsorbent |
-
2013
- 2013-03-14 CN CN201310081612.3A patent/CN104045548B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772156A (en) * | 1971-11-19 | 1973-11-13 | Monsanto Co | Purification of acetic acid streams by distillation |
| CN1041357A (en) * | 1988-09-27 | 1990-04-18 | Bp化学有限公司 | The removing method of iodine or iodide impurities |
| CN101811023A (en) * | 2010-03-11 | 2010-08-25 | 上海复旭分子筛有限公司 | Preparation method, product and applications thereof of acetate deep deiodination adsorbent |
Non-Patent Citations (1)
| Title |
|---|
| 孙晓轩、王斌: "清除甲醇羰基化合成醋酸中微量碘化物的方法", 《天然气化工》 * |
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