CN102911013B - Ethylene-glycolrefining method - Google Patents
Ethylene-glycolrefining method Download PDFInfo
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- CN102911013B CN102911013B CN201210448405.2A CN201210448405A CN102911013B CN 102911013 B CN102911013 B CN 102911013B CN 201210448405 A CN201210448405 A CN 201210448405A CN 102911013 B CN102911013 B CN 102911013B
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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 approximately 6.0% for frostproofer, tackiness agent, paint solvent, Everlube, tensio-active agent and polyester polyol etc. in addition.
At present, the synthetic oil that mainly contains of China's ethylene glycol synthesizes and two kinds of routes of Coal Chemical Industry.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.Make ethylene glycol product applications by coal-ethylene glycol product and petroleum path identical, 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 reach more than 99.9%, in product all in various degree exist with content beyond expression of wordsly, in 220nm ~ 350nm wavelength region, have the organic impurity of absorption.The existence of these impurity declines the ultraviolet permeability of 220nm ~ 350nm wavelength region, affects the quality of polyester, 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 researchs show, the impurity that affects ethylene glycol quality product is mainly some by products in production process.If the impurity in petroleum path ethylene glycol product is mainly some by products in oxidation of ethylene process, comprise the organic compound such as aldehyde, ketone.And impurity in the ethylene glycol product of Coal Chemical Industry Route is mainly some the micro-by products in dimethyl oxalate shortening and 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 have larger absorption in 220nm ~ 350nm wavelength regions, therefore reduce the content of these carbonyl compound impurity, improve the ultraviolet permeability of ethylene glycol product in 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 95% left and right at the ultraviolet permeability at wavelength 275nm place from 68.4%.But the H in the gac of pickling
+easily come off, make ethylene glycol aobvious acid, pollute ethylene glycol, and charcoal absorption amount is little, and regeneration difficulty, can not in reindustrialization, apply.
US4647705 disclose a kind of improve ethylene glycol ultraviolet permeability method, the method is under alkaline condition, using alumino nickel as catalyzer, industrial ethylene glycol hydrogenation is stirred and processed for three days, ethylene glycol after treatment 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 to be greater than the UV-irradiation industry ethylene glycol of 220nm, makes the impurity conversion that contains multiple pairs of keys in ethylene glycol, improves the ultraviolet permeability of ethylene glycol.The ethylene glycol amount of above-mentioned two kinds of method processing is little, long processing period and complex operation, and efficiency is too low, cannot realize large-scale continuous production.
US5770777 discloses a kind of method that reduces ethylene glycol or aqueous glycol solution uv-absorbing, the method is processed the method for ethylene glycol finished product with strongly basic anion exchange resin or the weak anion exchange resin with 5% ~ 10% highly basic center, improved 20% through the ethylene glycol of the method processing at the ultraviolet permeability at wavelength 275nm place.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, underpressure distillation again after plastic resin treatment, ethylene glycol is greater than 90% at the ultraviolet permeability of wavelength 220nm, is greater than 97% at the ultraviolet permeability at wavelength 275nm place.CN1580020A discloses a kind of process for refining and purifying of ethylene glycol, and the method is by ethylene glycol successively by a kind of slightly acidic chelating Zeo-karb and storng-acid cation exchange resin, and in ethylene glycol, aldehyde and iron ion content can reduce greatly.Above-mentioned disclosed patented method can improve the ultraviolet permeability of ethylene glycol in wavelength 220nm ~ 350nm scope, but these three kinds of methods have all only been used single functional resin acid or alkalescence, it is only simple acid-base catalysis, these methods are applicable to for the purifying ethylene glycol effect taking oil as waste that only contains aldehyde type impurities, but be difficult to obtain ideal effect for the ethylene glycol product purification taking coal as waste that contains ester class and ketone impurity, the known effective ways that ester group in ethylene glycol and ketone group are reduced into hydroxyl are that reductive agent is joined in ethylene glycol, after completing, passes through again question response to filter, washing, the methods such as rectifying are removed remaining reductive agent, because ethylene glycol at a certain temperature is easily oxidized to aldehyde, so in fact, in ethylene glycol, add the method for reductive agent to be difficult to be implemented industrial.
The present invention is creationary to be loaded to corresponding reductive agent respectively in solid acid alkali catalytic agent and makes dual-function catalyst, and difunctional solid acid alkali catalytic agent is coordinated and made simultaneously, reaches the object of ethylene glycol deep refining.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of difunctional solid acid catalyst and difunctional solid base catalyst of adopting to be used in conjunction with, through catalysis, the method for reduction reaction to purifying ethylene glycol, the catalyzer using not only has the general character of acid-base catalysis, due to the introducing of reductive agent, make catalyzer also there is reductibility.The aldehyde compound of the trace in 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 ethylene glycol and ketone impurity 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 petroleum path ethylene glycol product, can remove again micro-ester group and keto compounds impurity in 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, it is the catalyst equipment through solid acid catalyst and solid base catalyst series connection by the ethylene glycol from industrial product route, by reduction and the katalysis of catalyzer, the carbonyl compound class trace impurity that affects ultraviolet permeability in 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 does not limit.
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, hydrazonium sulfate; The preferably mixture of one or more in hydrazine hydrate, mercapto-amine, iron protochloride or hydrazonium sulfate.
0 ~ 40%wt that in difunctional solid acid catalyst of the present invention, the charge capacity of reductive agent is carrier, preferably 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, lithium aluminum hydride; The preferably mixture of one or both in Sodium Nitrite or sodium borohydride.
0 ~ 40%wt that in difunctional solid base catalyst of the present invention, the charge capacity of reductive agent is carrier, preferably 0.5 ~ 25%wt, more preferably 0.5 ~ 10%wt.
The ethylene glycol from industrial product route described in the inventive method is preferably from the Coal Chemical Industry Route of prior art or the ethylene glycol of petroleum path.
Compared with the exquisite method of purification of existing ethylene glycol product, tool of the present invention has the following advantages:
1, the present invention adopts difunctional solid acid catalyst and difunctional solid base catalyst, conversion that can not only catalysis aldehyde compound, can also reduce to ester group and keto compounds, and its catalytic effect significantly improves compared with other method.Through the ultraviolet permeability of method of the present invention ethylene glycol after treatment at 220nm>80%, 275nm>94%, 350nm>99%.
2, the present invention adopts reductive agent is loaded in solid acid alkali catalytic agent, does not have the separation problem again 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 petroleum path ethylene glycol, and can remove the ester class in coal-ethylene glycol product, the carbonyl impurities such as cyclic diketones material and conjugation aldehyde of replacement.
4, the method operational management is convenient.
Embodiment
Following instance is only to further illustrate the present invention, is not restriction the scope of protection of the invention.
Embodiment 1
Get commercially available acidic molecular sieve H-Y100g, add 40% hydrazine hydrate 5g, obtain difunctional solid acid catalyst through ordinary method load, get commercially available polystyrene basic anion exchange resin D201 100g, add Sodium Nitrite 2g, obtain difunctional solid acid catalyst through ordinary method load; Difunctional solid acid catalyst is packed into
glass tubing reactor in as catalyticreactor I, difunctional solid base catalyst is packed into
glass tubing reactor in as catalyticreactor II, after ethylene glycol product from Coal Chemical Industry Route is preheating to required extraction temperature, squeeze into reactor with pump, make it successively by catalyticreactor I and the catalyticreactor II of series connection, catalytic temperature is 45 DEG C, pressure is 1MPa, and air speed is 4h
-1, what obtain the results are shown in Table 1.
Embodiment 2
Get commercially available acidic molecular sieve H-Y100g, add 40% hydrazine hydrate 5g, obtain difunctional solid acid catalyst through ordinary method load, get commercially available polystyrene basic anion exchange resin D201 100g, add Sodium Nitrite 5g, obtain difunctional solid acid catalyst through ordinary method load; Difunctional solid base catalyst is packed into
glass tubing reactor in as catalyticreactor I, difunctional solid acid catalyst is packed into
glass tubing reactor in as catalyticreactor II, Coal Chemical Industry Route ethylene glycol product is squeezed into reactor with pump after being preheating to required extraction temperature, makes it successively by catalyticreactor I and the catalyticreactor II of series connection, and catalytic temperature is 45 DEG C, pressure is 1MPa, and air speed is 4h
-1, what obtain the results are shown in Table 1.
Embodiment 3
Get commercially available polystyrene acidic cation-exchange resin D001 100g, add 40% hydrazine hydrate 7.5g, obtain difunctional solid acid catalyst through ordinary method load, get commercially available polystyrene basic anion exchange resin D201 100g, add Sodium Nitrite 3g, obtain difunctional solid acid catalyst through ordinary method load; Other are with embodiment 1, and what obtain 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 ordinary method load, get commercially available polystyrene basic anion exchange resin D201 100g, add sodium borohydride 1.5g, obtain difunctional solid acid catalyst through ordinary method load; Other are with embodiment 1, and what obtain 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 ordinary method load, get commercially available alkali alumina 100g, add Sodium Nitrite 10g, obtain difunctional solid acid catalyst through ordinary method load; Other are with embodiment 1, and what obtain 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 ordinary method load, get commercially available alkaline molecular sieve 100g, add sodium borohydride 5g, obtain difunctional solid acid catalyst through ordinary method load; Other are with embodiment 1, and what obtain the results are shown in Table 1:
Embodiment 7
Get commercially available polystyrene acidic cation-exchange resin D001 50g, add 40% hydrazine hydrate 5g, obtain difunctional solid acid catalyst a through ordinary method load, get commercially available acidic molecular sieve H-Y50g, add 40% hydrazine hydrate 5g, obtain difunctional solid acid catalyst b through ordinary method load, get commercially available alkaline molecular sieve 100g, add sodium borohydride 3g, obtain difunctional solid acid catalyst through ordinary method load; Two kinds of difunctional solid acid catalysts are mixed and packed into
glass tubing reactor in as catalyticreactor I, difunctional solid base catalyst is packed into
glass tubing reactor in as catalyticreactor II, other are with embodiment 1, what obtain the results are shown in Table 1:
Embodiment 8
Ethylene glycol changes the ethylene glycol product from petroleum path into by the ethylene glycol product from Coal Chemical Industry Route, and other are with embodiment 3, and what obtain the results are shown in Table 1:
Comparative example 1
Not loading catalyst of catalyticreactor I, catalyticreactor II filling polystyrene basic anion exchange resin D201 100g, the other the same as in Example 1, what obtain the results are shown in Table 1.
Comparative example 2
Catalyticreactor I filling polystyrene acidic cation-exchange resin D001 100g, not loading catalyst of catalyticreactor II, the other the same as in Example 1, what obtain the results are shown in Table 1.
Comparative example 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, what obtain the results are shown in Table 1.
Each embodiment and comparative example process after to the ultraviolet permeability data that obtain of ethylene glycol analysis in 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 example 1 | 55.92 | 83.58 | 97.72 |
| Comparative example 2 | 56.25 | 82.66 | 96.89 |
| Comparative example 3 | 60.12 | 85.67 | 96.95 |
Note: ethylene glycol transmitance is measured and pressed GB/T 14571.4-2008.
As can be seen from Table 1, the present invention coordinates the catalyst system of catalysis, reduction stronger than using the catalytic activity of 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 ethylene glycol product, reduce the content of carbonyl compound, the ultraviolet permeability of ethylene glycol after treatment is at 220nm>80%, 275nm>94%, 350nm>99%.
Claims (12)
1. the method for a deep refining ethylene glycol, it is characterized in that: under conventional reaction conditions, catalyst equipment by the ethylene glycol from industrial product route through solid acid catalyst and solid base catalyst series connection, by reduction and the katalysis of catalyzer, the carbonyl compound class trace impurity that affects ultraviolet transmittance in 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 does not limit.
2. method claimed in claim 1, is characterized in that: described difunctional solid acid catalyst be load have reductive agent 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 one or more the mixture in cuprous chloride, iron protochloride, mercapto-amine, hydrazine, hydrazine hydrate, monomethylhydrazine, 1,1 dimethylhydrazine, phenylhydrazine or 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 hydrazonium sulfate.
5. method claimed in claim 2, is characterized in that: 0.5～25%wt that in described difunctional solid acid catalyst, the charge capacity of reductive agent is carrier.
6. method claimed in claim 2, is characterized in that: 0.5～10%wt that in described difunctional solid acid catalyst, the charge capacity of reductive agent is carrier.
7. method claimed in claim 1, is characterized in that: described difunctional solid base catalyst be load have reductive agent alkaline molecular sieve, alkali alumina or anionite-exchange resin in one or more mixture.
8. method claimed in claim 7, 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, lithium aluminum hydride.
9. method claimed in claim 8, 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 sodium borohydride.
10. method claimed in claim 7, is characterized in that: 0.5～25%wt that in described difunctional solid base catalyst, the charge capacity of reductive agent is carrier.
11. method claimed in claim 7, is characterized in that: 0.5～10%wt that in described difunctional solid base catalyst, the charge capacity of reductive agent is carrier.
12. method claimed in claim 1, is characterized in that: the 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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| CN105622348B (en) | 2014-11-28 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of separation method of the close polyol blends of boiling point |
| 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 |
| 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 |
| 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 |
| CN109704927B (en) * | 2017-10-25 | 2021-08-03 | 中国石油化工股份有限公司 | Method for hydrofining and purifying diethylene 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 |
| CN112441882B (en) * | 2019-09-02 | 2023-04-07 | 中国石油化工股份有限公司 | Stabilizer for refining ethylene glycol and preparation method thereof |
| CN112439412B (en) * | 2019-09-02 | 2023-06-06 | 中国石油化工股份有限公司 | Refining agent for ethylene glycol hydrofining 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 |
| 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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| EP1160228B1 (en) * | 2000-05-31 | 2006-07-12 | Shell Internationale Researchmaatschappij B.V. | Process for separating ethylene glycol |
| CN1249000C (en) * | 2003-08-05 | 2006-04-05 | 中国石化上海石油化工股份有限公司 | Etharediol refined purifying method |
| CN102649688B (en) * | 2011-02-25 | 2014-08-13 | 中国石油化工股份有限公司 | Method for purifying ethylene glycol product |
| CN102649704B (en) * | 2011-02-25 | 2015-02-11 | 中国石油化工股份有限公司 | Method for purifying ethylene glycol product |
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