CN103121934A - Method for reducing iodide impurity content in acetic acid - Google Patents
Method for reducing iodide impurity content in acetic acid Download PDFInfo
- Publication number
- CN103121934A CN103121934A CN2011103697184A CN201110369718A CN103121934A CN 103121934 A CN103121934 A CN 103121934A CN 2011103697184 A CN2011103697184 A CN 2011103697184A CN 201110369718 A CN201110369718 A CN 201110369718A CN 103121934 A CN103121934 A CN 103121934A
- Authority
- CN
- China
- Prior art keywords
- acetic acid
- ion exchange
- idodine
- exchange resin
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for reducing iodide impurity content in acetic acid. The technical problem that the method for reducing iodide impurity content in acetic acid is poor in deiodination effect in the prior art is mainly solved. The method comprises the following steps: allowing acetic acid containing the iodide impurity to flow through a deiodination agent bed layer, wherein the deiodination agent is obtained by carrying out an ion exchange reaction between a sulfonic acid type macroporous ion exchange resin and a silver compound, the sulfonic acid type macroporous ion exchange resin has a macroporous styrene-divinyl benzene copolymer framework and -SO3H, and -SO3H is connected with a benzene ring in the copolymer framework through -CH2-. According to the technical scheme, the problem is better solved, and the method can be used for refining production of acetic acid containing iodide impurity.
Description
Technical field
The present invention relates to a kind of method that reduces iodide impurities content in acetic acid.
Background technology
Ion exchange resin take vinylbenzene-divinylbenzene crosslink multipolymer as skeleton is divided into gel-type and macroporous type with pore structure character, and is divided into anionic and cationic with the charge property of cation exchange groups in ion exchange resin.In order to prepare macroreticular ion exchange resin, usually at first carrying out vinylbenzene and divinylbenzene suspension polymerization under the existence of pore-creating agent prepares macropore vinylbenzene-divinylbenzene crosslink multipolymer (this field is called for short making large-pore white balls used, can buy from a lot of ion exchange resin manufacturers), for example, " containing synthesizing and characterizing of two keys wide aperture styrene-divinylbenzene microballoon " (applied chemistry [J], 1998,15 (2): reported making large-pore white balls used preparation method 103-105).And then as required the making large-pore white balls used chemical modification of carrying out is obtained containing macroporous cation or the anionite-exchange resin that negatively charged ion or positively charged ion etc. have ion exchanging function.
In prior art, take vinylbenzene--the divinylbenzene crosslink multipolymer is the sulfonic group (SO of the sulfonic acid type macroporous ion exchange resin of skeleton
3H) with this resin in phenyl ring directly be connected, can by under the existence of swelling agent, use dense H
2SO
4Perhaps SO
3Making large-pore white balls usedly carry out sulfonation and obtain described Deng sulphonating agent commonly used.For example, " sulfonation of porous vinylbenzene one divinyl benzene copolymer microballoon and to the absorption of bovine serum albumin " (ion-exchange and absorption [J], 2010,26 (4): 334-34) and " sulfonation reaction of high Crosslinked Macroporous styrene-divinylbenzene copolymer " (ion-exchange and absorption [J], 2000,16 (1): the method for sulfonating of having reported making large-pore white balls used resin 1-8).This sulfonic acid type macroporous ion exchange resin all has sale at home and abroad.
In order to obtain take vinylbenzene--the divinylbenzene crosslink multipolymer is the macroporous anion exchange resin of skeleton, the commonly used chloromethylation reagent such as available chlorine methyl ether carries out modification to making large-pore white balls used, obtain connecting on phenyl ring the vinylbenzene of chloromethyl--divinylbenzene crosslink multipolymer (macropore chlorine ball is called for short in this field), for example, " polystyrene chloromethylation Investigation on Technological Conditions " (Yindu Journal (certainly attaining the science version) [J], 1993,3:44-53) reported the preparation technology of chlorine ball, then the chlorine ball can obtain macroporous anion exchange resin with the amine reaction.
In addition, point out in " tensio-active agent and washing composition chemistry and technology " ([M] China Light Industry Press Beijing 1997 May the 1st edition 287 pages), alkyl chloride and sulphite reaction can obtain alkylsulfonate, and this reaction is called the Strecker reaction, and its reaction formula is as follows:
RCH
2Cl+Na
2SO
3→RCH
2SO
3Na+NaCl
US Patent No. 2115192 also disclose adopt the Strecker reaction with in compound-CH
2-Cl groups converted is-CH
2SO
3M, wherein M is K, Na etc.
As a kind of purposes of sulfonic acid type macroporous ion exchange resin, by with Ag ion exchange after obtain containing silver resin and take off idodine, this takes off idodine and can be used for removing iodine in carbonyl process acetic acid.For example, US 4,615, and 806 disclose employing sulfonic acid type macroporous ion exchange resin and AgNO
3, CH
3COOAg carries out ion-exchange and obtains argentiferous and take off idodine, disclose simultaneously this has been taken off idodine for reducing the method for iodide impurities content in acetic acid, the sulfonic acid type macroporous ion exchange resin that adopts in embodiment is take Amberlyst 15 as representative, and its sulfonic group directly is connected with phenyl ring in styrene diethylene benzene copoly mer.But in the disclosed reduction acetic acid of prior art, the method for iodide impurities content is taken off the iodine weak effect.
Summary of the invention
Technical problem to be solved by this invention is the problem that the method for iodide impurities content in the reduction acetic acid that exists in prior art is taken off the iodine weak effect, the method of iodide impurities content in a kind of new reduction acetic acid is provided, and the method has the effective characteristics of iodine of taking off.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method that reduces iodide impurities content in acetic acid, comprise by the acetic acid that contains iodide impurities is flowed through and take off the idodine bed, the described idodine of taking off is obtained by ion exchange reaction by sulfonic acid type macroporous ion exchange resin and silver compound, described sulfonic acid type macroporous ion exchange resin have macropore styrene diethylene benzene copoly mer skeleton and-SO
3H is characterized in that described-SO
3H passes through-CH
2-be connected with phenyl ring in described copolymer skeleton.
The styrene diethylene benzene copoly mer of macropore described in the technique scheme skeleton content of Vinylstyrene unit by weight percentage is preferably 8～28%; The specific surface of described sulfonic acid type macroporous ion exchange resin is preferably 200～400m
2/ g, pore volume is preferably 0.4～0.6cm
3/ g; The quality complete exchange capacity of described sulfonic acid type macroporous ion exchange resin is preferably 3.4～5.3mmol/g; The ratio that the described silver-colored exchange capacity that takes off idodine accounts for complete exchange capacity is preferably 9% to 75%; Described temperature of taking off the idodine bed can from the fusing point of the acetic acid that contains iodide impurities to boiling point, be preferably 45 ℃ to 115 ℃, more preferably 90 ℃ to 115 ℃; The described acetic acid that the contains iodide impurities air speed of taking off the idodine bed of flowing through is preferably 4～10h
-1The described iodide that contain are preferably idoalkane, have 1～8 carbon atom in its molecule.
The preparation method of the sulfonic acid type macroporous ion exchange resin described in the inventive method comprises the steps:
(1) with the macropore styrene diethylene benzene copoly mer that is connected with chloromethyl on phenyl ring in reaction solvent with M
2SO
3React and obtain the ion exchange resin precursor I, wherein M is selected from Na, K, and wherein said reaction solvent is methyl-sulphoxide and/or water;
(2) with described ion exchange resin precursor I with the dilute aqueous soln of strong acid process, the pure water washing obtains described sulfonic acid type macroporous ion exchange resin.
The described reaction solvent of step in above-mentioned preparation method (1) forms by weight percentage and is preferably: dimethyl sulfoxide (DMSO) 70～90%, water 10～30%; The cl content that is connected with on phenyl ring in the macropore styrene diethylene benzene copoly mer of chloromethyl is preferably 14～20% by weight percentage; The temperature of reaction of step (1) is preferably 150～170 ℃, and the reaction times is preferably 4～8 hours; Step (1) is connected with the macropore styrene diethylene benzene copoly mer of chloromethyl in chlorine, with M
2SO
3Mol ratio be preferably 1: 1.05～1.2; M in step (1)
2SO
3Be preferably 1: 5 with the weight ratio of described reaction solvent～10.
The present invention reduces the method for iodide impurities content in acetic acid, owing to taking off in the sulfonic acid type macroporous ion exchange resin that idodine adopts-SO
3H passes through-CH
2-indirectly be connected with phenyl ring in described copolymerization skeleton, make this take off the in use harsh environment for use of tolerance more of idodine.Can find out from the experimental result that table 6 embodiment 10 to 13 and comparative example 1 to 4 provide, take off the idodine evaluation experimental under 45 ℃, the inventive method and comparative example are close, but the inventive method bring up to 90 ℃ to 115 ℃ take off the iodine temperature time, taking off the iodine effect obviously improves along with the raising of temperature, and the iodine effect of taking off of Comparative Examples improves the trend that is variation with temperature under condition on year-on-year basis, for example in the embodiment 13 rear acetic acid of processing, iodine content is 1.2ppb, and on year-on-year basis in situation the iodine content of Comparative Examples 4 up to 15.1ppb, obtained technique effect preferably.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
1, making large-pore white balls used preparation
With reference to " containing synthesizing and characterizing of two keys wide aperture styrene-divinylbenzene microballoon " (applied chemistry [J], 1998,15 (2): 103-105) carry out.Add in polymeric kettle under room temperature 450 grams through the vinylbenzene of underpressure distillation, (content is 49.5% to 590 gram technical grade Vinylstyrenes, all the other are vinyl xylene, ethyl vinyl benzene), 1560 gram pore-creating agents (being the toluene solution of the linear polystyrene (number-average molecular weight Mn=9.8 ten thousand) of 15% (weight)), 8 gram benzoyl peroxides, stirring and dissolving.Add the aqueous solution 2000ml that contains gum arabic 2% (weight) and polyvinyl alcohol (polymerization degree 1750. alcoholysis degrees 88%) 2% (weight), stir lower logical nitrogen 30min.Carried out suspension polymerization 10 hours under 88 ℃ under stirring.Suction filtration, water and toluene wash filter cake each 3 times.Take toluene as solvent extraction 24 hours, 60 ℃ of lower vacuum-dryings 48 hours, get 1019 gram styrene diethylene benzene copoly mer microballoons (namely making large-pore white balls used).Making large-pore white balls used middle Vinylstyrene content is 28% (weight).With technical grade Vinylstyrene consumption, pore-creating agent consumption, and making large-pore white balls used middle Vinylstyrene content is listed in table 1.
2, the preparation of macropore chlorine ball
Reference " polystyrene chloromethylation Investigation on Technological Conditions " (Yindu Journal (certainly attaining the science version) [J], 1993,3:44-53) carry out.Add making large-pore white balls used that 500 gram steps 1 obtain in enamel reaction still, (molecular formula is Cl-CH to add 3000 gram chloromethyl methyl ethers
2-O-CH
3), swelling 6 hours slowly adds Zinc Chloride Anhydrous 195 grams under stirring, be warming up to 40 ℃ of reactions 10 hours, filter, filter cake washing with alcohol 2 times, washing with acetone 2 times, under room temperature, vacuum-drying is 48 hours, obtains chloromethylation macropore styrene diethylene benzene copoly mer (being macropore chlorine ball).Through ultimate analysis, cl content is 19.8% (weight).The cl content of chloromethyl methyl ether consumption, reaction times and macropore chlorine ball is listed in table 2.
3, the preparation of sulfonic acid type macroporous ion exchange resin
(1) ion exchange resin precursor I preparation
With reference to US 2115192.Macropore chlorine ball 500 grams, 387 gram Na that step 2 is obtained
2SO
3(be M
2SO
3Be Na
2SO
3, in chlorine, macropore chlorine ball and M
2SO
3Mol ratio be 1: 1.1), 3100 gram water (be that reaction solvent is water, M
2SO
3With the weight ratio of reaction solvent be 1: 8), add in the magnetic agitation autoclave, under stirring 160 ℃ the reaction 6 hours, be down to room temperature, filter, with deionized water wash to filtrate to the reaction that is negative of 1% silver nitrate aqueous solution, the filter cake that obtains is the ion exchange resin precursor I.With M in the preparation of ion exchange resin precursor I
2SO
3Kind, macropore chlorine ball and M
2SO
3Mol ratio, reaction solvent form, M
2SO
3List in table 3 with weight ratio, temperature of reaction, the reaction times of reaction solvent.
(2) be converted into sulfonic acid type macroporous ion exchange resin of the present invention by the ion exchange resin precursor I
The ion exchange resin precursor I that step (1) is obtained whole soak ten times with the aqueous hydrochloric acid of 5% (weight), use 2000 milliliters of described hydrochloric acid solns at every turn, each 6 hours, stir once in every 30 minutes between soak period.Then filter, with deionized water wash to filtrate, 1% silver nitrate aqueous solution is neutral, obtain sulfonic acid type macroporous ion exchange resin aqueous resins of the present invention, 50 ℃ of vacuum-dryings obtained the dry thing of sulfonic acid type macroporous ion exchange resin of the present invention in 24 hours.Record quality complete exchange capacity (being also the butt complete exchange capacity) according to GB GB8144-87 method and be 3.42mmol/g.
The dry thing of the sulfonic acid type macroporous ion exchange resin that step (2) is obtained, the specific surface that gets dried resin with the low temperature nitrogen determination of adsorption method are 397, pore volume is 0.58; Through ultimate analysis, the sulphur content of dried resin is 11.3% (weight).Suppose that the chlorine in step (1) and (2) precursor I all is converted into sulfonic group, the sulphur theoretical content of the dried resin that calculate this moment is 18.3% (weight).The sulfonic group productive rate that calculates according to the formula of sulfonic group productive rate=(the sulphur theoretical content of the sulphur content/dried resin of dried resin) * 100% is 61.7%.The sulfonic group productive rate is higher, shows that the reaction of step (1) is higher to generating sulfonic selectivity, and is more favourable to preparation sulfonic acid type macroporous ion exchange resin.The character of sulfonic acid type macroporous ion exchange resin is listed in table 4.
4, take off the preparation of idodine
With reference to US 4,615,806 carry out.Get dry thing 100 grams of sulfonic acid type macroporous ion exchange resin that step (2) obtains, add 1000 ml deionized water, add 5.65 gram Silver Nitrates, stirred 12 hours, filtering, is neutral with deionized water washing leaching cake to filtrate, and 50 ℃ of vacuum-dryings obtain taking off the dry thing of idodine.Take the dry thing that takes off idodine as benchmark, through ultimate analysis, silver content is 3.43% by weight percentage.With the silver compound kind, the silver compound consumption that adopt and take off in idodine the character such as silver content and list in table 5.
5, take off the evaluation of idodine
Get and take off dry thing 25 grams of idodine in above-mentioned steps 3, the internal diameter of packing into is that 2.5 centimetres, length are in the chromatographic column of vertical placement of 20 centimetres, with respect to taking off idodine volume 4h
-1Air speed (annotate: air speed refers to the quality of taking off the acetic acid that idodine per hour processes of unit mass.) contain the acetic acid of methyl iodide 200ppb with peristaltic pump in iodine from chromatographic column top injection, controlling the interior acetic acid temperature of chromatographic column is 90 ℃, treated acetic acid is from chromatographic column bottom outflow, when outflow acetic acid reaches 250 gram, from the acetic acid spout sampling of chromatographic column, be 7.1ppb through the gas chromatography determination iodine content.Evaluation temperature, the iodine content that contains iodine acetic acid air speed and acetic acid sample are listed in table 6.
[embodiment 2～13]
1, making large-pore white balls used preparation
Except technical grade Vinylstyrene consumption and the variation of pore-creating agent consumption, all the step 1 with embodiment 1 is identical for other.With technical grade Vinylstyrene consumption, pore-creating agent consumption, and making large-pore white balls used middle Vinylstyrene content is listed in table 1.
2, the preparation of macropore chlorine ball
Except adopting making large-pore white balls used in step 1, beyond chloromethyl methyl ether consumption and reaction times changed, all the step 2 with embodiment 1 was identical for other.The cl content of chloromethyl methyl ether consumption, reaction times and macropore chlorine ball is listed in table 2.
3, the preparation of sulfonic acid type macroporous ion exchange resin
(1) ion exchange resin precursor I preparation
Except the macropore chlorine ball in employing step 2, and M
2SO
3Kind, macropore chlorine ball and M
2SO
3Mol ratio, reaction solvent form, M
2SO
3Outside changing with weight ratio, temperature of reaction, reaction times of reaction solvent, operate identical with step (1) in embodiment 1 step 3.The Main change condition is listed in table 3.
(2) be converted into the sulfonic acid type macroporous ion exchange resin by the ion exchange resin precursor I
Except the ion exchange resin precursor I that adopts step (1) preparation, operation steps is identical with step (2) in embodiment 1 step 3, and the specific nature of sulfonic acid type macroporous ion exchange resin is listed in table 4.
embodiment 1 to embodiment 6 only changes solvent and the experiment that do not change other condition can be found out from table 3 and table 4, it is that the sulfonic group productive rate of solvent ratio when adopting water to be solvent is high that DMSO is adopted in the reaction of preparation precursor I, the resin quality complete exchange capacity that makes is corresponding also high, and when mixed solvent that the water that adopts by 70～90% (weight) dimethyl sulfoxide (DMSO) and 10～30% (weight) forms, further when mixed solvent that the water that adopts by 85～90% (weight) dimethyl sulfoxide (DMSO) and 10～15% (weight) forms, sulfonic group productive rate and the resin quality complete exchange capacity that makes are higher, has better technique effect.
4, take off the preparation of idodine
Except adopting the sulfonic acid type macroporous ion exchange resin of step (2) preparation, and outside the silver compound kind, the silver compound consumption that adopt changed, other operation steps was with embodiment 1 step 4.With the silver compound kind, the silver compound consumption that adopt and take off in idodine the character such as silver content and list in table 5.
5, take off the evaluation of idodine
Except adopting the idodine of taking off of step 4 preparation, and evaluation temperature, contain outside iodine acetic acid air speed changes, other operation steps is with the step 5 of embodiment 1.Evaluation temperature, the iodine content that contains iodine acetic acid air speed and acetic acid sample are listed in table 6.
[embodiment 14]
Replace containing the acetic acid of methyl iodide 200ppb in iodine except step 5 adopts the acetic acid that contains 1-iodine octane 200ppb in iodine, other operation steps is all identical with embodiment 13.
[comparative example 1]
1, making large-pore white balls used preparation
With the step 1 in embodiment 1.
2, the preparation of sulfonic acid type macroporous ion exchange resin
(ion-exchange and absorption [J], 2000,16 (1): method 1-8) is carried out with reference to " sulfonation reaction of high Crosslinked Macroporous styrene-divinylbenzene copolymer ".Be specially: add making large-pore white balls used in 500 gram steps 1 in the enamel sulphonation kettle, add 1000 milliliters of ethylene dichloride, under room temperature standing 24 hours, then add 98% the vitriol oil 1000 grams, under stirring, first 83 ℃ of reactions 3 hours, then reacted again 5 hours at 110 ℃.After reaction finishes, reaction mixture is down to room temperature, filter, with washing with acetone 3 times, each 1000 milliliters, acetone of washing, then deionized water wash to washings is negative to 5% barium chloride solution, obtains sulfonic acid type macroporous ion exchange resin aqueous resins, then obtains the dry thing of sulfonic acid type macroporous ion exchange resin in 24 hours 50 ℃ of vacuum-dryings.
3, take off the preparation of idodine
Except the dry thing of the sulfonic acid type macroporous ion exchange resin that adopts step 2 preparation, and the consumption of Silver Nitrate is beyond 28.43 grams, other operation is all identical with step 4 in embodiment 1, with silver compound kind, the silver compound consumption of employing and take off in idodine the character such as silver content and list in table 5.
4, take off the evaluation of idodine
Except adopting the idodine of taking off of step 3 preparation, evaluation temperature is beyond 45 ℃, and other appreciation condition is identical with embodiment 1 step 5.The iodine content of concrete evaluation temperature, acetic acid air speed and acetic acid sample is listed in table 6.
[comparative example 2～4]
Except the evaluation temperature in step 4 changed, other operation was identical with comparative example 1, and the iodine content of concrete evaluation temperature, acetic acid air speed and acetic acid sample is listed in table 6.
Can find out from table 6 embodiment 10 to 13 and comparative example 1 to 4, take off the idodine evaluation experimental under 45 ℃, the inventive method and comparative example are close, but when the inventive method is brought up to the evaluation temperature of 90 ℃ to 115 ℃, the iodine effect of taking off of taking off idodine obviously improves along with the raising of temperature, and the iodine effect of taking off of Comparative Examples improves the trend that is variation with temperature under condition on year-on-year basis.
[comparative example 5]
Replace containing the acetic acid of methyl iodide 200ppb in iodine except step 4 adopts the acetic acid that contains 1-iodine octane 200ppb in iodine, other operation steps is all identical with comparative example 4.
The preparation that table 1 is making large-pore white balls used
The preparation of table 2 macropore chlorine ball
| The chloromethyl methyl ether consumption, g | Reaction times, h | The cl content of macropore chlorine ball, % (weight) | |
| Embodiment 1 | 3000 | 10 | 19.8 |
| Embodiment 2 | 3000 | 10 | 19.8 |
| Embodiment 3 | 3000 | 10 | 19.8 |
| Embodiment 4 | 3000 | 10 | 19.8 |
| Embodiment 5 | 3000 | 10 | 19.8 |
| Embodiment 6 | 3000 | 10 | 19.8 |
| Embodiment 7 | 3000 | 10 | 19.8 |
| Embodiment 8 | 2500 | 7 | 18.5 |
| Embodiment 9 | 2100 | 5 | 14.2 |
| Embodiment 10 | 2100 | 5 | 14.2 |
| Embodiment 11 | 2100 | 5 | 14.2 |
| Embodiment 12 | 2100 | 5 | 14.2 |
| Embodiment 13 | 2100 | 5 | 14.2 |
| Embodiment 14 | 2100 | 5 | 14.2 |
| Comparative example 1 | -- | -- | -- |
| Comparative example 2 | -- | -- | -- |
| Comparative example 3 | -- | -- | -- |
| Comparative example 4 | -- | -- | -- |
| Comparative example 5 | -- | -- | -- |
The preparation of table 3 ion exchange resin precursor I
★DMSO represents dimethyl sulfoxide (DMSO).
The character of table 4 sulfonic acid type macroporous ion exchange resin
▲The sulphur theoretical content of butt resin, % (weight)=[(cl content * sulfur atomic weight of macropore chlorine ball/chlorine nucleidic mass)/(cl content * sulfur atomic weight of the cl content of 100-macropore chlorine ball+macropore chlorine ball/chlorine nucleidic mass)] * 100%.
Table 5 takes off the preparation of idodine
☆Take off silver content in idodine * 1000/[silver atoms amount (taking off silver content in idodine in 1-table 5) in silver exchange capacity=table 5];
△The silver exchange capacity accounts for complete exchange capacity ratio=(the quality complete exchange capacity in the silver-colored exchange capacity in table 5/table 4) * 100%.
Table 6 takes off the evaluation of idodine
| Evaluation temperature, ℃ | Contain iodine acetic acid air speed ◇，h -1 | The iodine content of acetic acid sample, ppb | |
| Embodiment 1 | 90 | 4 | 7.1 |
| Embodiment 2 | 90 | 4 | 6.9 |
| Embodiment 3 | 90 | 4 | 6.5 |
| Embodiment 4 | 90 | 10 | 7.3 |
| Embodiment 5 | 100 | 8 | 2.1 |
| Embodiment 6 | 100 | 8 | 0.8 |
| Embodiment 7 | 100 | 8 | 0.5 |
| Embodiment 8 | 115 | 8 | 0.5 |
| Embodiment 9 | 115 | 8 | 1.1 |
| Embodiment 10 | 45 | 4 | 3.1 |
| Embodiment 11 | 90 | 4 | 2.4 |
| Embodiment 12 | 100 | 4 | 1.7 |
| Embodiment 13 | 115 | 4 | 1.2 |
| Embodiment 14 | 115 | 4 | 1.9 |
| Comparative Examples 1 | 45 | 4 | 3.2 |
| Comparative Examples 2 | 90 | 4 | 5.4 |
| Comparative Examples 3 | 100 | 4 | 12.2 |
| Comparative Examples 4 | 115 | 4 | 15.1 |
| Comparative Examples 5 | 115 | 4 | 15.7 |
◇Refer to the quality of taking off the acetic acid that idodine per hour processes of unit mass.
Claims (9)
1. method that reduces iodide impurities content in acetic acid, comprise by the acetic acid that contains iodide impurities is flowed through and take off the idodine bed, the described idodine of taking off is obtained by ion exchange reaction by sulfonic acid type macroporous ion exchange resin and silver compound, described sulfonic acid type macroporous ion exchange resin have macropore styrene diethylene benzene copoly mer skeleton and-SO
3H is characterized in that described-SO
3H passes through-CH
2-be connected with phenyl ring in described copolymer skeleton.
2. the method for iodide impurities content in reduction acetic acid according to claim 1, it is characterized in that described macropore styrene diethylene benzene copoly mer skeleton by weight percentage the content of Vinylstyrene unit be 8～28%.
3. the method for iodide impurities content in reduction acetic acid according to claim 1, the specific surface that it is characterized in that described sulfonic acid type macroporous ion exchange resin is 200～400m
2/ g, pore volume are 0.4～0.6cm
3/ g.
4. the method for iodide impurities content in reduction acetic acid according to claim 1 and 2, the quality complete exchange capacity that it is characterized in that described sulfonic acid type macroporous ion exchange resin is 3.4～5.3mmol/g.
5. the method for iodide impurities content in reduction acetic acid according to claim 1, is characterized in that the ratio that the described silver-colored exchange capacity that takes off idodine accounts for complete exchange capacity is 9% to 75%.
6. the method for iodide impurities content in reduction acetic acid according to claim 1, the temperature that it is characterized in that taking off the idodine bed is 45 ℃ to 115 ℃.
7. the method for iodide impurities content in reduction acetic acid according to claim 6, the temperature that it is characterized in that taking off the idodine bed is 90 ℃ to 115 ℃.
8. the method for iodide impurities content in reduction acetic acid according to claim 1 is characterized in that the described acetic acid that the contains iodide impurities air speed of taking off the idodine bed of flowing through is 4～10h
-1
9. the method for iodide impurities content in reduction acetic acid according to claim 1, is characterized in that the described iodide that contain are idoalkane, has 1～8 carbon atom in its molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110369718.4A CN103121934B (en) | 2011-11-18 | 2011-11-18 | Method for reducing iodide impurity content in acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110369718.4A CN103121934B (en) | 2011-11-18 | 2011-11-18 | Method for reducing iodide impurity content in acetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103121934A true CN103121934A (en) | 2013-05-29 |
| CN103121934B CN103121934B (en) | 2014-07-23 |
Family
ID=48453121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110369718.4A Active CN103121934B (en) | 2011-11-18 | 2011-11-18 | Method for reducing iodide impurity content in acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103121934B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108349864A (en) * | 2015-11-13 | 2018-07-31 | 国际人造丝公司 | Purification acetic acid and the method for making acid anhydrides be hydrated |
| CN114210370A (en) * | 2021-12-20 | 2022-03-22 | 南京亘闪生物科技有限公司 | Preparation method of catalyst microspheres for preparing ethyl acetate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2115192A (en) * | 1936-06-20 | 1938-04-26 | Rohm & Haas | Aryloxy polyalkylene ether sulphonates |
| US4615806A (en) * | 1985-03-07 | 1986-10-07 | Celanese Corporation | Removal of iodide compounds from non-aqueous organic media |
| CN1061956A (en) * | 1990-10-19 | 1992-06-17 | 英国石油有限公司 | From carboxylic acid and/or carboxylic acid anhydride, remove the method for iodine compound |
| CN101209428A (en) * | 2006-12-28 | 2008-07-02 | 江苏索普（集团）有限公司 | Adsorption agent for removing iodide from organic medium and preparation and application |
-
2011
- 2011-11-18 CN CN201110369718.4A patent/CN103121934B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2115192A (en) * | 1936-06-20 | 1938-04-26 | Rohm & Haas | Aryloxy polyalkylene ether sulphonates |
| US4615806A (en) * | 1985-03-07 | 1986-10-07 | Celanese Corporation | Removal of iodide compounds from non-aqueous organic media |
| US4615806B1 (en) * | 1985-03-07 | 1994-05-03 | Hoechst Co American | Removal of iodide compounds from non-aqueous organic media |
| CN1061956A (en) * | 1990-10-19 | 1992-06-17 | 英国石油有限公司 | From carboxylic acid and/or carboxylic acid anhydride, remove the method for iodine compound |
| CN101209428A (en) * | 2006-12-28 | 2008-07-02 | 江苏索普（集团）有限公司 | Adsorption agent for removing iodide from organic medium and preparation and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108349864A (en) * | 2015-11-13 | 2018-07-31 | 国际人造丝公司 | Purification acetic acid and the method for making acid anhydrides be hydrated |
| US10899696B2 (en) | 2015-11-13 | 2021-01-26 | Celanese International Corporation | Processes for purifying acetic acid and hydrating anhydride |
| CN108349864B (en) * | 2015-11-13 | 2021-04-13 | 国际人造丝公司 | Process for purifying acetic acid and hydrating anhydrides |
| CN114210370A (en) * | 2021-12-20 | 2022-03-22 | 南京亘闪生物科技有限公司 | Preparation method of catalyst microspheres for preparing ethyl acetate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103121934B (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103122044B (en) | Sulphonic acid type macroporous ion exchange resin and preparation method thereof | |
| CN101735372B (en) | Chelate resin and production method and application thereof | |
| CN1865302A (en) | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method | |
| CN102295723B (en) | 6-aminopyridine-3-carboxylic acid chelating resin and its preparation method | |
| CN1935861A (en) | N-methyl, N-carboxymethyl dithio amidocarbonic acid chelating resin and its preparing method | |
| CN109482162A (en) | A kind of chromatography media and preparation method thereof | |
| CN103785358A (en) | Materials used for extracting lithium from brine, and method | |
| CN103121934B (en) | Method for reducing iodide impurity content in acetic acid | |
| CN110117379B (en) | Adsorbing material for removing LDL (low density lipoprotein) in blood perfusion and preparation method thereof | |
| CN100560617C (en) | A kind of N, two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl) and preparation method thereof | |
| CN103122043B (en) | Preparation method of deiodination agent | |
| CA2641370C (en) | Amphoteric ion exchangers | |
| CN102079721B (en) | Torasemide compound and new preparation method thereof | |
| CN101190974A (en) | Pyrrolidone-base modified composite function absorption resin and preparation method thereof | |
| CN1238111C (en) | High exchange capacity resin catalyst and its preparation method | |
| US8062526B2 (en) | Separation of platinum group metals | |
| CN109772449B (en) | Polystyrene-immobilized polyethylene glycol and imidazole coordination ionic liquid modified by derivative thereof | |
| CN104087749A (en) | Silica gel extraction agent containing quaternary ammonium positive ions and salicylaldoxime | |
| CN106582579A (en) | Four-oxygen naphthalene mixed cup [2] arene [2] triazine bonded silica gel stationary phase and preparation method and application thereof | |
| CN105541561B (en) | A kind of synthesis of 1,1,1 3 (4 hydroxy phenyl) ethane and purification process | |
| CN102060762B (en) | Montelukast compound and new preparation method thereof | |
| CN112237898B (en) | Strong anion type solid phase extraction column filler and preparation method thereof | |
| CN102008978B (en) | Chiral catalyst and preparation method and application thereof | |
| CN101307019B (en) | Method for preparing N-amino-3-azabicyclo[3,3,0]octane hydrochloride | |
| CN1204963C (en) | Aromatic hydrocarbon linked silica gel solid phase and its preparation and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |