CN1580020A - Etharediol refined purifying method - Google Patents
Etharediol refined purifying method Download PDFInfo
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- CN1580020A CN1580020A CN 03142064 CN03142064A CN1580020A CN 1580020 A CN1580020 A CN 1580020A CN 03142064 CN03142064 CN 03142064 CN 03142064 A CN03142064 A CN 03142064A CN 1580020 A CN1580020 A CN 1580020A
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- ethylene glycol
- exchange resin
- catalyst
- refining
- fixed bed
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Abstract
The invention refers to a kind of refining method of glycol to emerge the aldehyde-containing impurities in the products of the glycol industry. The glycol passes through the static bed of catalyst I and the static bed of catalyst II in order at the refining temperature of between 25deg.C and 60deg.C and at the speed of between 3hr-1 and 12 hr-1. The two static bed of catalyst is filled with cation exchange resin A and B. The A is a kind of faintly acid chelated cation exchange resin, whose surface is spud with the functional group of -NR1R2. The R1 and R2 is selected from the hydroxyl of between C1 and C3 or a kind of radical in the sulph carboxyl of between C1 and C3. The B is a kind of highly acidic exchange resin, whose surface is spud with the functional group of -SO3H. The key of the invention lies in making the glycol pass through the static bed of catalyst I to remove the metallic ions, which protects the highly acidic cation exchange resin in the static bed of catalyst II from being affected by the metallic ions to keep good activity of getting rid of the aldehyde.
Description
Technical field
The present invention relates to a kind of process for refining and purifying of ethylene glycol, particularly make ethylene glycol by catalyst fixed bed layer to remove the ethylene glycol process for refining and purifying that contains aldehyde compound that wherein exists.
Background technology
Ethylene glycol is the important Chemicals that are only second to polyethylene and polyvinyl chloride in the ethylene industry derivative, its purposes is very extensive, one of them very important purposes is that this generally is called as fibre-grade ethylene glycol product as the basic raw material that is used to make the polyester (PET) of trevira.The technology that the production of present industrial ethylene glycol mostly adopts ethylene epoxidizing and then hydration to produce ethylene glycol, continuity along with the production run time, particularly in later stage of oxide catalyst operation, because the decline of ethylene oxide catalyst performance, usually by strengthening the throughput that reaction conditions comes assurance device, therefore this often cause containing in the product increase of aldehyde radical by product.Weigh a uv absorption rate that important indicator is the 220hm place of fibre-grade ethylene glycol quality product, because it will influence the gloss and the colourity of downstream polyester product.It has been generally acknowledged that the important factor that influences fibre-grade ethylene glycol product 220nm place uv absorption rate be exist in the product contain the aldehyde radical by product, therefore make a purification that important step is an ethylene glycol of fibre-grade ethylene glycol product, to remove the aldehyde compound that contains wherein.
Generally adopt ion exchange resin to make with extra care purification ethylene glycol in the prior art as catalyzer, as United States Patent (USP) 6, it is catalyzer that a kind of storng-acid cation exchange resin is adopted in 242,655 introductions, and the aldehyde group content of ethylene glycol product is reduced to below the 5ppm by 20ppm.Yet the defective of these existent method is aldehyde group contents of ethylene glycol product can only be removed to about 2ppm at the most, and the 220nm place uv absorption rate of ethylene glycol product does not reach a very ideal numerical value yet at this moment.
Summary of the invention
The invention provides a kind of process for refining and purifying of ethylene glycol, the technical problem that it will solve is that the aldehyde group content of ethylene glycol product is reduced to below the 2ppm, thereby obtains more high-quality ethylene glycol product.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of process for refining and purifying of ethylene glycol, this method comprise makes ethylene glycol successively by catalyst fixed bed layer I and catalyst fixed bed layer II, and extraction temperature is 25～60 ℃, and liquid hourly space velocity is 3～12hr
-1, catalyst fixed bed layer I filling male ion-exchange resin A, catalyst fixed bed layer II filling male ion-exchange resin B.
Zeo-karb A is a kind of slightly acidic chelating Zeo-karb, and its surface anchoring contains structure and is-NR
1R
2Functional group, R
1, R
2Take from C separately
1～C
3Carboxyl or C
1～C
3A kind of group in the thiocarboxyl group, optimal scheme is R
1, R
2Be acetoxyl or thioacetic acid base, and R
1With R
2Identical;
Zeo-karb B is a storng-acid cation exchange resin, and its surface anchoring contains structure and is-SO
3The functional group of H.
Above-mentioned extraction temperature is preferably 30～50 ℃, and liquid hourly space velocity is preferably 4～7hr
-1
Catalyzer can adopt the ordinary method preparation.Slightly acidic chelating Zeo-karb generally is the styrene polymer bead with divinylbenzene crosslink to be carried out nitrated, and repeated hydrogenation is reduced into amine, and and chloroacetate reaction, behind thorough washing, drying to water content is 0～1% to pack and get final product.Storng-acid cation exchange resin preparation is simple relatively, carries out sulfonation with the vitriol oil earlier, and after washing, drying to water content is 0～1% to pack.
The refining effect of ethylene glycol removes outside the Pass performance with catalyzer has, also be decided by extraction temperature and ethylene glycol reaction conditionss such as liquid hourly space velocity by catalyst fixed bed layer, more than the reaction conditions contriver of Tui Jianing thinks very ideal, reaction conditions outside this scope can carry out the refining of ethylene glycol equally, but refining effect is relatively poor relatively.
Contriver back by experiment finds, can contain metal ions such as iron, nickel, chromium, the equipment that these metal ions are contacted from the ethylene glycol production process in the ethylene glycol product usually.And acidic cation-exchange resin be easy to inactivation after metal ion contacts, thereby reduction is removed the ability that contains aldehyde compound.Key of the present invention is to allow ethylene glycol earlier by above-mentioned catalyst fixed bed layer I, and the slightly acidic chelating Zeo-karb that loads among the catalyst fixed bed layer I can remove metal ion effectively, this has just guaranteed that the storng-acid cation exchange resin among the catalyst fixed bed layer II keeps good activity, and the quality that removes further raising ethylene glycol product of ethylene glycol metal ion neutralization product also is very useful.This shows that the present invention compared with prior art has obvious improvement.
Below will the invention will be further described by specific embodiment.
In embodiment and comparative example, without refining ethylene glycol product purity of purifying is 99.98%, wherein aldehyde group content is 10ppm, iron ion content is that (because usually the metal ion that contains in the ethylene glycol product is mainly iron ion, so embodiment and comparative example are only measured the variation of iron ion content before and after refining the purification to 10ppm.)。
Embodiment
[embodiment 1～8]
The 40 gram slightly acidic chelating Zeo-karbs of packing in φ 25mm * 765mm glass tubular reactor, its surface anchoring contain structure and are-N (CH
2COOH)
2Functional group, constitute catalyst fixed bed layer I.And then loading 100 gram storng-acid cation exchange resins, its surface anchoring contains structure and is-SO
3The functional group of H constitutes catalyst fixed bed layer II.The reactor outside is incubated with recirculated water.Ethylene glycol is squeezed into reactor with pump after being preheated to required extraction temperature, makes it successively by catalyst fixed bed layer I and catalyst fixed bed layer II.
[embodiment 9]
Constitute the slightly acidic chelating Zeo-karb of catalyst fixed bed layer I, its surface anchoring contains structure and is-N (CH
2COOH) (CH
2COSH) functional group, all the other are with embodiment 1～8.
[comparative example]
Do not have catalyst fixed bed layer I in the reactor, all the other are with embodiment 1～8.
The extraction temperature that each embodiment and comparative example are concrete and the liquid hourly space velocity of control, and the ethylene glycol after handling is analyzed the index that obtains see Table 1.
Table 1.
| Extraction temperature (℃) | Liquid hourly space velocity (hr -1) | Aldehyde group content (ppm) | Fe ion content (ppm) | |
| Embodiment 1 | ????30 | ????4 | ?????1.3 | ?????0.9 |
| Embodiment 2 | ????25 | ????4 | ?????1.4 | ?????1.3 |
| Embodiment 3 | ????35 | ????4 | ?????1.2 | ?????1.6 |
| Embodiment 4 | ????55 | ????4 | ?????1.4 | ?????1.8 |
| Embodiment 5 | ????60 | ????3 | ?????1.0 | ?????0.9 |
| Embodiment 6 | ????48 | ????12 | ?????1.8 | ?????2.2 |
| Embodiment 7 | ????40 | ????8 | ?????1.2 | ?????2.4 |
| Embodiment 8 | ????50 | ????10 | ?????1.7 | ?????2.6 |
| Embodiment 9 | ????48 | ????7 | ?????1.5 | ?????2.0 |
| Comparative example | ????40 | ????8 | ?????2.1 | ????10 |
Annotate:
Aldehyde group content and Fe ion content all adopt spectrophotometry, and wherein the mensuration of aldehyde group content is pressed the o-phenanthroline method, and the mensuration of Fe ion content is pressed GB/T14571.3-93.
Claims (4)
1, a kind of process for refining and purifying of ethylene glycol, this method comprise makes ethylene glycol successively by catalyst fixed bed layer I and catalyst fixed bed layer II, and extraction temperature is 25～60 ℃, and liquid hourly space velocity is 3～12hr
-1, catalyst fixed bed layer I filling male ion-exchange resin A, catalyst fixed bed layer II filling male ion-exchange resin B,
Zeo-karb A is a kind of slightly acidic chelating Zeo-karb, and its surface anchoring contains structure and is-NR
1R
2Functional group, R
1, R
2Take from C separately
1～C
3Carboxyl or C
1～C
3A kind of group in the thiocarboxyl group;
Zeo-karb B is a storng-acid cation exchange resin, and its surface anchoring contains structure and is-SO
3The functional group of H.
2, the process for refining and purifying of ethylene glycol according to claim 1 is characterized in that described Zeo-karb A surface anchoring contains structure and is-NR
1R
2Functional group, R
1, R
2Be acetoxyl or thioacetic acid base, and R
1With R
2Identical.
3, the process for refining and purifying of ethylene glycol according to claim 1 is characterized in that described extraction temperature is 30～50 ℃.
4, the process for refining and purifying of ethylene glycol according to claim 1 is characterized in that described liquid hourly space velocity is 4～7hr
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03142064 CN1249000C (en) | 2003-08-05 | 2003-08-05 | Etharediol refined purifying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03142064 CN1249000C (en) | 2003-08-05 | 2003-08-05 | Etharediol refined purifying method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1580020A true CN1580020A (en) | 2005-02-16 |
| CN1249000C CN1249000C (en) | 2006-04-05 |
Family
ID=34579353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03142064 Expired - Lifetime CN1249000C (en) | 2003-08-05 | 2003-08-05 | Etharediol refined purifying method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1249000C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219641A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for purifying ethylene glycol |
| CN102276418A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Ethylene glycol purification method |
| CN102911013A (en) * | 2012-11-09 | 2013-02-06 | 凯瑞化工股份有限公司 | Ethylene-glycolrefining method |
| CN106278821A (en) * | 2016-10-12 | 2017-01-04 | 凯瑞环保科技股份有限公司 | A kind of remove the method and device of plurality of impurities in ethylene glycol |
| CN109293475A (en) * | 2018-11-15 | 2019-02-01 | 北京兴高化学技术有限公司 | Coal-ethylene glycol refining methd and system |
| CN110052294A (en) * | 2019-04-18 | 2019-07-26 | 中峰化学有限公司 | Metal ion removes filter in isopropanol water solution |
| CN112441882A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Stabilizer for refining ethylene glycol and preparation method thereof |
| CN112441880A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Aldehyde removing agent for glycol aldehyde removing and refining and method for glycol aldehyde removing and refining |
-
2003
- 2003-08-05 CN CN 03142064 patent/CN1249000C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219641A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for purifying ethylene glycol |
| CN102219641B (en) * | 2010-04-15 | 2013-07-31 | 中国石油化工股份有限公司 | Method for purifying ethylene glycol |
| CN102276418A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Ethylene glycol purification method |
| CN102276418B (en) * | 2010-06-11 | 2013-07-31 | 中国石油化工股份有限公司 | Ethylene glycol purification method |
| CN102911013A (en) * | 2012-11-09 | 2013-02-06 | 凯瑞化工股份有限公司 | Ethylene-glycolrefining method |
| CN106278821A (en) * | 2016-10-12 | 2017-01-04 | 凯瑞环保科技股份有限公司 | A kind of remove the method and device of plurality of impurities in ethylene glycol |
| CN106278821B (en) * | 2016-10-12 | 2019-01-25 | 凯瑞环保科技股份有限公司 | The method and device of plurality of impurities in a kind of removing ethylene glycol |
| CN109293475A (en) * | 2018-11-15 | 2019-02-01 | 北京兴高化学技术有限公司 | Coal-ethylene glycol refining methd and system |
| CN110052294A (en) * | 2019-04-18 | 2019-07-26 | 中峰化学有限公司 | Metal ion removes filter in isopropanol water solution |
| CN112441882A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Stabilizer for refining ethylene glycol and preparation method thereof |
| CN112441880A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Aldehyde removing agent for glycol aldehyde removing and refining and method for glycol aldehyde removing and refining |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1249000C (en) | 2006-04-05 |
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