CN102911013A - Ethylene-glycolrefining method - Google Patents
Ethylene-glycolrefining method Download PDFInfo
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- CN102911013A CN102911013A CN2012104484052A CN201210448405A CN102911013A CN 102911013 A CN102911013 A CN 102911013A CN 2012104484052 A CN2012104484052 A CN 2012104484052A CN 201210448405 A CN201210448405 A CN 201210448405A CN 102911013 A CN102911013 A CN 102911013A
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Abstract
The invention provides an ethylene-glycol deep-refining method which comprises the following steps: allowing ethylene-glycol from an industrial production line to pass through catalyst equipment where a solid-acid catalyst and a solid-alkali catalyst are connected in series; and after the reduction and catalytic action of the catalysts, converting trace impurities (such as carbonyl compounds) in ethylene-glycol, which affects ultraviolet light transmittance, into saturation materials that does not absorb ultraviolet light, wherein the solid-acid catalyst is a difunctional solid-acid catalyst which has functions of reduction and acid catalysis, and the solid-alkali catalyst a difunctional solid-alkali catalyst which has functions of reduction and alkali catalysis; and the solid-acid catalyst and the solid-alkali catalyst are in random serial connection. According to the invention, the ultraviolet light transmittance of ethylene-glycol subjected to processing by the method is larger than 80 percent at wavelength of 220 nm, 94 percent at wavelength of 275 nm and 99 percent at wavelength of 350 nm.
Description
Technical field
The present invention relates to a kind of method of deep refining ethylene glycol.
Technical background
Ethylene glycol (EG) is a kind of important Organic Chemicals, mainly for the production of polyester, deicing fluid, tackiness agent, paint solvent, Everlube, tensio-active agent and polyester polyol etc.Wherein polyester is the main consumer field of China's ethylene glycol, and its consumption accounts for 94.0% of gross domestic consumption amount, and about 6.0% is used for frostproofer, tackiness agent, paint solvent, Everlube, tensio-active agent and polyester polyol etc. in addition.
At present, synthetic synthetic and two kinds of routes of Coal Chemical Industry of oil that mainly contain of China's ethylene glycol.Traditional petroleum path is by petroleum cracking ethene processed, then through oxidation of ethylene, and the legal explained hereafter ethylene glycol of epoxyethane water.Novel Coal Chemical Industry synthesizing glycol route is by producing synthesis gas from coal oxidative coupling reaction producing oxalic ester, then further Hydrogenation ethylene glycol.It is identical to make the ethylene glycol product applications by coal-ethylene glycol product and petroleum path, and the quality standard of ethylene glycol product of therefore weighing two kinds of routes is also identical.
Although the purity of the ethylene glycol product of China's oil route and Coal Chemical Industry Route can both reach more than 99.9%, in the product all in various degree exist with content beyond expression of wordsly, the organic impurity of absorption is arranged in 220nm ~ 350nm wavelength region.The existence of these impurity descends the ultraviolet permeability of 220nm ~ 350nm wavelength region, affects the quality of polyester, such as the gloss of fiber, colourity, painted and hardness etc.Therefore the quality of ethylene glycol depends primarily on ultraviolet permeability value index.
A large amount of studies show that the impurity that affects the ethylene glycol quality product mainly is some by products in the production process.Mainly be some by products in the oxidation of ethylene process such as the impurity in petroleum path ethylene glycol product, comprise the organic compound such as aldehyde, ketone.And the impurity in the ethylene glycol product of Coal Chemical Industry Route mainly is some the micro-by products in dimethyl oxalate shortening and the high temperature aerobic treating process, comprising: the cyclic diketones of ester class and replacement and a small amount of conjugation aldehyde material.And these contain carbonyl impurities larger absorption are arranged in 220nm ~ 350nm wavelength region, therefore reduce the content of these carbonyl compound impurity, improve the ethylene glycol product at the ultraviolet permeability of wavelength 220nm ~ 350nm scope, the quality that improves ethylene glycol is of great importance.
For petroleum path ethylene glycol product purification, it is enough to remove the patent of trace impurity wherein and report.WO99/58483 discloses a kind of method of ethylene glycol purification of improvement, the method adopts the gac of pickling to process ethylene glycol, this method can make ethylene glycol bring up to more than 76% from 43.9% at the ultraviolet permeability at wavelength 220nm place, brings up to about 95% from 68.4% at the ultraviolet permeability at wavelength 275nm place.But the H in the gac of pickling
+Come off easily, make ethylene glycol aobvious acid, pollute ethylene glycol, and the charcoal absorption amount is little, and the regeneration difficulty, can not use on the reindustrialization.
US4647705 disclose a kind of improve the ethylene glycol ultraviolet permeability method, the method is under alkaline condition, as catalyzer, industrial ethylene glycol hydrogenation is stirred processing in three days with alumino nickel, the ethylene glycol after the processing brings up to 81% at the ultraviolet permeability at wavelength 220nm place from 40%.US4289593 discloses a kind of method that improves UV transmittance of ethylene glycol, and the method utilizes wavelength greater than the UV-irradiation industry ethylene glycol of 220nm, makes the impurity conversion that contains a plurality of pairs of keys in the ethylene glycol, improves the ultraviolet permeability of ethylene glycol.The ethylene glycol amount that above-mentioned two kinds of methods are processed is little, long processing period and complex operation, and efficient is too low, can't realize large-scale continuous production.
US5770777 discloses a kind of method that reduces ethylene glycol or aqueous glycol solution uv-absorbing, the method is with strongly basic anion exchange resin or have the method for the weak anion exchange resin processing ethylene glycol finished product at 5% ~ 10% highly basic center, and the ultraviolet permeability of ethylene glycol at wavelength 275nm place of processing through the method improved 20%.US6525229 discloses a kind of separation method of ethylene glycol, the method is used strong basicity negative resin or strong acid positive resin, or be the mixture process ethylene glycol of Zeo-karb and anionite-exchange resin, again underpressure distillation after plastic resin treatment, ethylene glycol at the ultraviolet permeability of wavelength 220nm greater than 90%, at the ultraviolet permeability at wavelength 275nm place greater than 97%.CN1580020A discloses a kind of process for refining and purifying of ethylene glycol, and successively by a kind of slightly acidic chelating Zeo-karb and storng-acid cation exchange resin, aldehyde and iron ion content can reduce the method greatly in the ethylene glycol with ethylene glycol.Above-mentioned disclosed patented method can both improve ethylene glycol at the ultraviolet permeability of wavelength 220nm ~ 350nm scope, but these three kinds of methods have all only been used single functional resin acid or alkalescence, it only is simple acid-base catalysis, these methods are fit to for the purifying ethylene glycol effect take oil as waste that only contains aldehyde type impurities, but then be difficult to obtain ideal effect for the ethylene glycol product purification take coal as waste that contains ester class and ketone impurity, the known effective ways that ester group in the ethylene glycol and ketone group are reduced into hydroxyl are that reductive agent is joined in the ethylene glycol, after finishing, passes through again question response to filter, washing, the methods such as rectifying are removed remaining reductive agent, because ethylene glycol is oxidized to aldehyde easily at a certain temperature, so in fact, adding the method for reductive agent in the ethylene glycol is difficult to implement industrial obtaining.
The present invention then creationary reductive agent with correspondence loads to respectively in the solid acid alkali catalytic agent and makes dual-function catalyst, and difunctional solid acid alkali catalytic agent cooperated simultaneously so that, reach the purpose of ethylene glycol deep refining.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide the difunctional solid acid catalyst of a kind of employing and difunctional solid base catalyst to be used, through catalysis, the reduction reaction method to purifying ethylene glycol, the catalyzer that uses not only has the general character of acid-base catalysis, because the introducing of reductive agent makes catalyzer also have reductibility.The aldehyde compound of the trace in the ethylene glycol can be removed with ethylene glycol generation condensation reaction under the catalysis of strong acid or highly basic, and the ester class in the ethylene glycol and ketone impurity then rely on the reductibility of catalyzer to carry out reduction reaction and is converted into alcohols material.This invention can remove the aldehyde type impurities of trace in the petroleum path ethylene glycol product, can remove again micro-ester group and keto compounds impurity in the coal-ethylene glycol product, thereby significantly improve the ultraviolet transmittance of ethylene glycol.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of method of deep refining ethylene glycol is provided, will be from the ethylene glycol process solid acid catalyst of industrial product route and the catalyst equipment of solid base catalyst series connection, reduction and katalysis by catalyzer, the carbonyl compound class trace impurity that affects ultraviolet permeability in the ethylene glycol is converted into the non-absorbent saturate of UV-light, reduce the content of carbonyl compound, improve the ultraviolet permeability of ethylene glycol; Described solid acid catalyst is the difunctional solid acid catalyst with reduction and two kinds of functions of acid catalysis; Described solid base catalyst is the difunctional solid base catalyst with reduction and two kinds of functions of base catalysis; The order of described solid acid catalyst and solid base catalyst series connection without limits.
Difunctional solid acid catalyst of the present invention is the solid acid catalyst that load has the various prior aries of reductive agent, and preferred negative is loaded with one or more the mixture in acidic molecular sieve, acidic alumina or the Zeo-karb of reductive agent.
The reductive agent of difunctional solid acid catalyst of the present invention institute load is cuprous chloride, iron protochloride, mercapto-amine, hydrazine, hydrazine hydrate, monomethylhydrazine, 1, the mixture of one or more in 1-dimethylhydrazine, phenylhydrazine, the hydrazonium sulfate; The mixture of one or more in preferred hydrazine hydrate, mercapto-amine, iron protochloride or the hydrazonium sulfate.
The charge capacity of reductive agent is 0 ~ 40%wt of carrier in the difunctional solid acid catalyst of the present invention, preferred 0.5 ~ 25%wt, more preferably 0.5 ~ 10%wt.
Difunctional solid base catalyst of the present invention is the solid base catalyst that load has the various prior aries of reductive agent, and preferred negative is loaded with one or more the mixture in alkaline molecular sieve, alkali alumina or the anionite-exchange resin of reductive agent.
The reductive agent of difunctional solid base catalyst of the present invention institute load is one or more the mixture in Sodium Nitrite, sodium borohydride, the lithium aluminum hydride; The mixture of one or both in preferred Sodium Nitrite or the sodium borohydride.
The charge capacity of reductive agent is 0 ~ 40%wt of carrier in the difunctional solid base catalyst of the present invention, preferred 0.5 ~ 25%wt, more preferably 0.5 ~ 10%wt.
The described ethylene glycol from industrial product route of the inventive method is preferably from the Coal Chemical Industry Route of prior art or the ethylene glycol of petroleum path.
Compare with the exquisite method of purification of existing ethylene glycol product, the present invention has following advantage:
1, the difunctional solid acid catalyst and the difunctional solid base catalyst that adopt of the present invention, conversion that can not only the catalysis aldehyde compound can also be reduced to ester group and keto compounds, and its catalytic effect significantly improves than other method.The ultraviolet permeability of the ethylene glycol after method of the present invention is processed is at 220nm〉80%, 275nm〉94%, 350nm〉99%.
2, the present invention adopts reductive agent is loaded in the solid acid alkali catalytic agent, does not have the again separation problem of catalyzer and ethylene glycol, has avoided secondary pollution and the oxidation of ethylene glycol.Quality of glycol is guaranteed.
3, the method for purifying ethylene glycol of the present invention not only can remove aldehyde radical impurity in the petroleum path ethylene glycol, and can remove the carbonyl impurities such as the cyclic diketones material of ester class in the coal-ethylene glycol product, replacement and conjugation aldehyde.
4, the method operational management is convenient.
Embodiment
Following instance only is to further specify the present invention, is not the restriction the scope of protection of the invention.
Embodiment 1
Get commercially available acidic molecular sieve H-Y100g, the hydrazine hydrate 5g of adding 40% obtains difunctional solid acid catalyst through conventional method load, gets commercially available polystyrene basic anion exchange resin D201 100g, add Sodium Nitrite 2g, obtain difunctional solid acid catalyst through conventional method load; Difunctional solid acid catalyst is packed into
The Glass tubing reactor in as catalyticreactor I, difunctional solid base catalyst is packed into
The Glass tubing reactor in as catalyticreactor II, squeeze into reactor with pump after will being preheating to required extraction temperature from the ethylene glycol product of Coal Chemical Industry Route, make it successively by catalyticreactor I and the catalyticreactor II of series connection, catalytic temperature is 45 ℃, pressure is 1MPa, and air speed is 4h
-1, resultingly the results are shown in Table 1.
Embodiment 2
Get commercially available acidic molecular sieve H-Y100g, the hydrazine hydrate 5g of adding 40% obtains difunctional solid acid catalyst through conventional method load, gets commercially available polystyrene basic anion exchange resin D201 100g, add Sodium Nitrite 5g, obtain difunctional solid acid catalyst through conventional method load; Difunctional solid base catalyst is packed into
The Glass tubing reactor in as catalyticreactor I, difunctional solid acid catalyst is packed into
The Glass tubing reactor in as catalyticreactor II, squeeze into reactor with pump after Coal Chemical Industry Route ethylene glycol product is preheating to required extraction temperature, make it successively by catalyticreactor I and the catalyticreactor II of series connection, catalytic temperature is 45 ℃, pressure is 1MPa, and air speed is 4h
-1, resultingly the results are shown in Table 1.
Embodiment 3
Get commercially available polystyrene acidic cation-exchange resin D001 100g, the hydrazine hydrate 7.5g of adding 40%, obtain difunctional solid acid catalyst through conventional method load, get commercially available polystyrene basic anion exchange resin D201 100g, add Sodium Nitrite 3g, obtain difunctional solid acid catalyst through conventional method load; Other are with embodiment 1, resultingly the results are shown in Table 1:
Embodiment 4
Get commercially available acidic alumina 100g, add mercapto-amine 6g, obtain difunctional solid acid catalyst through conventional method load, get commercially available polystyrene basic anion exchange resin D201 100g, add sodium borohydride 1.5g, obtain difunctional solid acid catalyst through conventional method load; Other are with embodiment 1, resultingly the results are shown in Table 1:
Embodiment 5
Get commercially available polystyrene acidic cation-exchange resin D001 100g, add hydrazonium sulfate 5g, obtain difunctional solid acid catalyst through conventional method load, get commercially available alkali alumina 100g, add Sodium Nitrite 10g, obtain difunctional solid acid catalyst through conventional method load; Other are with embodiment 1, resultingly the results are shown in Table 1:
Embodiment 6
Get commercially available polystyrene acidic cation-exchange resin D001 100g, add iron protochloride 10g, obtain difunctional solid acid catalyst through conventional method load, get commercially available alkaline molecular sieve 100g, add sodium borohydride 5g, obtain difunctional solid acid catalyst through conventional method load; Other are with embodiment 1, resultingly the results are shown in Table 1:
Embodiment 7
Get commercially available polystyrene acidic cation-exchange resin D001 50g, the hydrazine hydrate 5g of adding 40%, obtain difunctional solid acid catalyst a through conventional method load, get commercially available acidic molecular sieve H-Y50g, the hydrazine hydrate 5g of adding 40% obtains difunctional solid acid catalyst b through conventional method load, gets commercially available alkaline molecular sieve 100g, add sodium borohydride 3g, obtain difunctional solid acid catalyst through conventional method load; Two kinds of difunctional solid acid catalysts are mixed pack into
The Glass tubing reactor in as catalyticreactor I, difunctional solid base catalyst is packed into
The Glass tubing reactor in as catalyticreactor II, other are with embodiment 1, resultingly the results are shown in Table 1:
Embodiment 8
Ethylene glycol changes ethylene glycol product from petroleum path into by the ethylene glycol product from Coal Chemical Industry Route, and other are with embodiment 3, resultingly the results are shown in Table 1:
Comparative Examples 1
Catalyticreactor I is loading catalyst not, catalyticreactor II filling polystyrene basic anion exchange resin D201 100g, and the other the same as in Example 1 resultingly the results are shown in Table 1.
Comparative Examples 2
Catalyticreactor I filling polystyrene acidic cation-exchange resin D001 100g, catalyticreactor II is loading catalyst not, and the other the same as in Example 1 resultingly the results are shown in Table 1.
Comparative Examples 3
Catalyticreactor I polystyrene basic anion exchange resin D201 100g, catalyticreactor II filling polystyrene acidic anionic exchange resin D001 100g, the other the same as in Example 1 resultingly the results are shown in Table 1.
The ultraviolet permeability data that obtain to the ethylene glycol analysis after each embodiment and comparative example are processed see Table 1.
Table 1
| Sequence number | 220nm （%） | 275nm （%） | 350nm （%） |
| Before processing (coal-ethylene glycol) | 50.63 | 75.28 | 96.57 |
| Before processing (oil preparing ethylene glycol) | 70.70 | 89.01 | 98.65 |
| Embodiment 1 | 80.65 | 94.52 | 99.52 |
| Embodiment 2 | 81.05 | 94.68 | 99.57 |
| Embodiment 3 | 83.27 | 95.81 | 99.89 |
| Embodiment 4 | 81.89 | 94.55 | 99.56 |
| Embodiment 5 | 81.52 | 94.63 | 99.62 |
| Embodiment 6 | 81.04 | 95.28 | 99.53 |
| Embodiment 7 | 80.18 | 94.25 | 99.28 |
| Embodiment 8 | 89.25 | 97.51 | 99.78 |
| Comparative Examples 1 | 55.92 | 83.58 | 97.72 |
| Comparative Examples 2 | 56.25 | 82.66 | 96.89 |
| Comparative Examples 3 | 60.12 | 85.67 | 96.95 |
Annotate: the ethylene glycol transmitance is measured and is pressed GB/T 14571.4-2008.
As can be seen from Table 1, the present invention cooperates the catalyst system of catalysis, reduction stronger than the catalytic activity of using single ordinary resin or two kinds of ordinary resin catalyzer with difunctional solid acid catalyst and difunctional solid base catalyst, can remove more thoroughly the carbonyl compound in the ethylene glycol product, reduce the content of carbonyl compound, the ultraviolet permeability of the ethylene glycol after the processing is at 220nm〉80%, 275nm〉94%, 350nm〉99%.
Claims (10)
1. the method for a deep refining ethylene glycol, it is characterized in that: under the reaction conditions of routine, will be from the ethylene glycol process solid acid catalyst of industrial product route and the catalyst equipment of solid base catalyst series connection, by reduction and the katalysis of catalyzer, the carbonyl compound class trace impurity that affects the ultraviolet transmittance in the ethylene glycol is converted into the non-absorbent saturate of UV-light; Described solid acid catalyst is the difunctional solid acid catalyst with reduction and two kinds of functions of acid catalysis; Described solid base catalyst is the difunctional solid base catalyst with reduction and two kinds of functions of base catalysis; The order of described solid acid catalyst and solid base catalyst series connection without limits.
2. method claimed in claim 1 is characterized in that: described difunctional solid acid catalyst be load reductive agent is arranged acidic molecular sieve, acidic alumina or Zeo-karb in one or more mixture.
3. method claimed in claim 2, it is characterized in that: the reductive agent of described difunctional solid acid catalyst institute load is cuprous chloride, iron protochloride, mercapto-amine, hydrazine, hydrazine hydrate, monomethylhydrazine, 1, the mixture of one or more in 1-dimethylhydrazine, phenylhydrazine or the hydrazonium sulfate.
4. method claimed in claim 3 is characterized in that: the reductive agent of described difunctional solid acid catalyst institute load is one or more the mixture in hydrazine hydrate, mercapto-amine, iron protochloride or the hydrazonium sulfate.
5. method claimed in claim 2, it is characterized in that: the charge capacity of reductive agent is 0 ~ 40%wt of carrier in the described difunctional solid acid catalyst; Preferred 0.5 ~ 25%wt; 0.5 ~ 10%wt most preferably.
6. method claimed in claim 1 is characterized in that: described difunctional solid base catalyst be load reductive agent is arranged alkaline molecular sieve, alkali alumina or anionite-exchange resin in one or more mixture.
7. method claimed in claim 6 is characterized in that: the reductive agent of described difunctional solid base catalyst institute load is one or more the mixture in Sodium Nitrite, sodium borohydride, the lithium aluminum hydride.
8. method claimed in claim 7 is characterized in that: the reductive agent of described difunctional solid base catalyst institute load is one or both the mixture in Sodium Nitrite or the sodium borohydride.
9. method claimed in claim 6, it is characterized in that: the charge capacity of reductive agent is 0 ~ 40%wt of carrier in the described difunctional solid base catalyst; Preferred 0.5 ~ 25%wt; 0.5 ~ 10%wt most preferably.
10. method claimed in claim 1, it is characterized in that: described ethylene glycol from industrial product route is from the Coal Chemical Industry Route of prior art or the ethylene glycol of petroleum path.
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| CN107973700A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | The method of ethylene glycol hydrofinishing |
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| 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 |
| CN112439412A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Refining agent for hydrofining of ethylene glycol and preparation method thereof |
| CN113493531A (en) * | 2020-04-01 | 2021-10-12 | 丹东明珠特种树脂有限公司 | Coal-based ethylene glycol impurity removal purification method, impurity removal type cation and anion exchange resin and preparation method thereof |
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| US9926251B2 (en) | 2014-11-28 | 2018-03-27 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for separation of close-boiling mixture of polyols |
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| 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 |
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| CN107970892B (en) * | 2016-10-21 | 2020-08-14 | 上海浦景化工技术股份有限公司 | Refining agent and preparation method and application thereof |
| CN107970892A (en) * | 2016-10-21 | 2018-05-01 | 上海浦景化工技术股份有限公司 | A kind of refining agent and its preparation method and application |
| CN107973700B (en) * | 2016-10-25 | 2021-02-05 | 中国石油化工股份有限公司 | Method for hydrofining ethylene glycol |
| CN107973700A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | The method of ethylene glycol hydrofinishing |
| CN109704927A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of method of diethylene glycol (DEG) hydrofinishing purification |
| 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 |
| 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 |
| CN112439412A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Refining agent for hydrofining of ethylene glycol and preparation method thereof |
| CN113493531A (en) * | 2020-04-01 | 2021-10-12 | 丹东明珠特种树脂有限公司 | Coal-based ethylene glycol impurity removal purification method, impurity removal type cation and anion exchange resin and preparation method thereof |
| CN113651776A (en) * | 2021-08-06 | 2021-11-16 | 中触媒新材料股份有限公司 | Purifying agent for compound containing aldehyde impurities and application thereof |
| CN113651776B (en) * | 2021-08-06 | 2023-10-17 | 中触媒新材料股份有限公司 | Purifying agent for aldehyde impurity-containing compound and application thereof |
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