CN102649692B - Improve the method for quality of glycol - Google Patents
Improve the method for quality of glycol Download PDFInfo
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- CN102649692B CN102649692B CN201110045323.9A CN201110045323A CN102649692B CN 102649692 B CN102649692 B CN 102649692B CN 201110045323 A CN201110045323 A CN 201110045323A CN 102649692 B CN102649692 B CN 102649692B
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Abstract
The present invention relates to a kind of method improving quality of glycol.Mainly solve in conventional art and there is the low technical problem of ethylene glycol product ultraviolet permeability.The present invention passes through to adopt ethylene glycol raw material, temperature 10 ~ 100 DEG C, and pressure 0.1 ~ 3.0MPa, air speed 0.2 ~ 5.0 hour
-1condition under by adsorption bed, with adsorbent contact, after absorption, obtain the effluent being rich in ethylene glycol; Wherein, sorbent material adopts at least one in ZSM-5, y-type zeolite or β zeolite, and silica alumina ratio is the technical scheme of 200 ~ 1000: 1, solves this problem preferably, can be used for improving in the industrial production of quality of glycol.
Description
Technical field
The present invention relates to a kind of method improving quality of glycol, particularly improve the method for quality of glycol about the product of Hydrogenation of Dimethyl Oxalate or oxalic acid diethyl ester Hydrogenation ethylene glycol.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, mainly for the production of trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used for coating in addition, soup, the industry such as brake fluid and ink, as solvent and the medium of ammonium pertorate, for the production of special solvent glycol ether etc., purposes is very extensive, one of them very important purposes is the basic raw material as the polyester (PET) for the manufacture of trevira, this is commonly referred to as fibre-grade ethylene glycol product.
At present, domestic and international large-scale ethylene glycol is produced and is mainly adopted petroleum path, both direct hydration method or the legal operational path of pressurized water, this technique is that oxyethane and water are made into mixed aqueous solution by 1: 20 ~ 22 (mol ratios), in 130 ~ 180 DEG C in fixed-bed reactor, react 18 ~ 30 minutes under 1.0 ~ 2.5MPa, oxyethane is all converted into alcohol mixture, the aqueous glycol solution content generated is greatly about 10% (massfraction), then to be separated with rectification under vacuum through multiple-effect evaporator dehydration concentrate and to obtain ethylene glycol, but production equipment need arrange multiple vaporizer, consume a large amount of energy and be used for dehydration, cause the technological process of production long, equipment is many and energy consumption is high.
At present, from world wide, petroleum resources day is becoming tight, and World oil price fluctuation is comparatively large, and the resource general layout of China can be summarized as few oil, weak breath, many coals.Development carbon one chemical industry not only can make full use of Sweet natural gas and coal resource, reduces the dependence of petroleum import and can alleviate environmental stress, is unusual important field of research.Being that barkite prepared by raw material with carbon monoxide, is then a very attractive Coal Chemical Industry Route by preparing glycol by hydrogenating oxalate.Now domestic and international to being that the research that barkite prepared by raw material achieves good effect with carbon monoxide, industrial production is ripe.And by preparing glycol by hydrogenating oxalate, still have more need of work to further investigate, especially in barkite hydrogenation process, by product is more, and the existence of the compound containing unsaturated double-bond of trace can affect the quality of ethylene glycol product.The important indicator weighing fibre-grade quality of ethylene glycol product is the UV-light transmittance at 220nm place, because it will affect gloss and the colourity of downstream polyester product.For petroleum path produce ethylene glycol it has been generally acknowledged that important factor affect fibre-grade ethylene glycol product 220nm place UV-light transmittance be exist in product contain aldehyde radical by product.And for the ethylene glycol product that hydrogenation of oxalate for preparing obtains, it is generally acknowledged that the important factor affecting ethylene glycol product 220nm place UV-light transmittance is different with petroleum path, less containing aldehyde radical by product under normal circumstances, and the carbonyl compound of other non-aldehyde radical may be the important factor affecting ethylene glycol product 220nm place UV-light transmittance.
Ion exchange resin is generally adopted to carry out refining purification ethylene glycol as catalyzer in the prior art, as United States Patent (USP) 6242655 introduction adopts a kind of storng-acid cation exchange resin to be catalyzer, the aldehyde group content of ethylene glycol product can be made after treatment to be reduced to below 5ppm by 20ppm.But the aldehyde group content that the defect of existing method is ethylene glycol product can only be removed to about 2ppm at the most, and now the 220nm place UV-light transmittance of ethylene glycol product still reaches an ideal numerical value in end, existing method is only applicable to the ethylene glycol product of petroleum path simultaneously, undesirable for coal-based product effect, and according to the title of existing report, coal-based ethylene glycol is generally less than 75 at its UV transmittance of 220nm place.Therefore, how to improve coal-based ethylene glycol product ultraviolet permeability, and then ensure that the quality of product is a very important research topic.And current rarely seen disclosed bibliographical information.
Summary of the invention
Technical problem to be solved by this invention is the technical problem that the ethylene glycol product ultraviolet permeability that exists in conventional art is low, provides a kind of method of raising quality of glycol newly.The method has ethylene glycol product ultraviolet permeability advantages of higher.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method improving quality of glycol, by ethylene glycol raw material, temperature 10 ~ 100 DEG C, and pressure 0.1 ~ 3.0MPa, air speed 0.2 ~ 5.0 hour
-1condition under by adsorption bed, with adsorbent contact, after absorption, obtain the effluent of ethylene glycol; It is characterized in that sorbent material adopts at least one in ZSM-5, y-type zeolite or β zeolite, silica alumina ratio is 200 ~ 1000: 1.
In technique scheme, sorbent material is preferably from ZSM-5 type zeolite, and silica alumina ratio preferable range is 300 ~ 800: 1.The preferred operations condition of adsorption bed is: temperature 20 ~ 80 DEG C, pressure 0.1 ~ 2.0MPa, air speed 0.5 ~ 3.0 hour
-1.
In technique scheme, ethylene glycol is from hydrogenation of oxalate for preparing ethylene glycol product.
As everyone knows, in hydrogenation of oxalate for preparing ethylene glycol reaction process, except ethylene glycol target product, also containing a certain amount of by product, as the ethanol of constant, butyleneglycol, the compound containing unsaturated double-bond of propylene glycol and other trace, and the method passing through conventional separation or other special extract rectification can remove the compound of most constant, as ethanol and propylene glycol etc., the purity of product is made to reach more than 99.8%, but, typically, although the purity of ethylene glycol is very high, but the 220nm of ethylene glycol product, 275nm and 350nm place UV-light transmittance still end reaches an ideal numerical value (requirement of national standard ethylene glycol top grade product is 220nm of ethylene glycol product, 275nm and 350nm place UV-light transmittance is greater than 75 respectively, 95 and 98), trace it to its cause and be, the trace impurity of the even ppm level of trace on the impact of product UV-light transmittance significantly, and the trace impurity of these ppm levels is more difficult removing typically by rectifying.
The discovery that present inventor is surprised under study for action, adopt ZSM-5, y-type zeolite or β zeolite to be sorbent material, have higher adsorption selectivity to trace impurity in ethylene glycol, especially ZSM-5 zeolite is better.The inventive method, adsorption separation efficiency is high, and technique is simple, is easy to accomplish scale production.
Adopt technical scheme of the present invention, with barkite hydrogenation ethylene glycol solution for raw material, adopt at least one in ZSM-5, y-type zeolite or β zeolite to be sorbent material, temperature 10 ~ 100 DEG C, pressure 0.1 ~ 3.0MPa, air speed 0.2 ~ 5.0 hour
-1condition under by adsorption bed, with adsorbent contact, the 220nm place UV-light transmittance of the ethylene glycol product obtained after absorption is greater than 75,275nm place UV-light transmittance and is greater than 95,350nm place UV-light transmittance and is greater than 98, achieves good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1 ~ 9]
300 grams of ZSM-5 type zeolite (its silica alumina ratio is 600: 1) sorbent materials are loaded in adsorption bed, passing into without refining ethylene glycol weight content is 99.85%, 220nm place UV-light transmittance is 25,275nm place UV-light transmittance is 92,350nm place UV-light transmittance is the solution of 98, adsorb under the condition shown in following table, after absorption, the result obtained is as follows:
Table 1
[embodiment 10]
500 grams of ZSM-5 type zeolite (its silica alumina ratio is 800: 1) sorbent materials are loaded in adsorption bed, passing into without refining ethylene glycol weight content is 99.95%, 220nm place UV-light transmittance is 15,275nm place UV-light transmittance is 90,350nm place UV-light transmittance is the solution of 98, temperature 25 DEG C, pressure 0.8MPa, air speed 5 hours
-1condition under by adsorption bed, adsorb with adsorbent contact, after absorption, the adsorbent solution 220nm place UV-light transmittance obtained is 80,275nm place UV-light transmittance be 96,350nm place UV-light transmittance is 99.
[embodiment 11]
500 grams of ZSM-5 type zeolite (its silica alumina ratio is 450: 1) sorbent materials are loaded in adsorption bed, passing into without refining ethylene glycol weight content is 99.98%, 220nm place UV-light transmittance is 5,275nm place UV-light transmittance is 91,350nm place UV-light transmittance is the solution of 98, temperature 90 DEG C, pressure 2.0MPa, air speed 3.5 hours
-1condition under by adsorption bed, adsorb with adsorbent contact, after absorption, the adsorbent solution 220nm place UV-light transmittance obtained is 78,275nm place UV-light transmittance be 95,350nm place UV-light transmittance is 100.
[embodiment 12]
500 grams of y-type zeolite (its silica alumina ratio is 200: 1) sorbent materials are loaded in adsorption bed, passing into without refining ethylene glycol weight content is 99.98%, 220nm place UV-light transmittance is 50,275nm place UV-light transmittance is 85,350nm place UV-light transmittance is the solution of 96, at temperature 70 C, pressure 1.5MPa, air speed 1.5 hours
-1condition under by adsorption bed, adsorb with adsorbent contact, after absorption, the adsorbent solution 220nm place UV-light transmittance obtained is 82,275nm place UV-light transmittance be 96,350nm place UV-light transmittance is 100.
[embodiment 13]
500 grams of zeolite beta (its silica alumina ratio is 260: 1) sorbent materials are loaded in adsorption bed, passing into without refining ethylene glycol weight content is 99.92%, 220nm place UV-light transmittance is 30,275nm place UV-light transmittance is 88,350nm place UV-light transmittance is the solution of 97, at temperature 50 C, pressure 0.8MPa, air speed 0.5 hour
-1condition under by adsorption bed, adsorb with adsorbent contact, after absorption, the adsorbent solution obtained is: the adsorbent solution 220nm place UV-light transmittance obtained is 78,275nm place UV-light transmittance be 95,350nm place UV-light transmittance is 99.
[comparative example 1]
According to each step and the operational condition of embodiment 10, the full gear ion exchange resin loading 500 grams of oil ethylene processes conventional in adsorption bed is sorbent material, passing into without refining ethylene glycol weight content is 99.95%, 220nm place UV-light transmittance is 15,275nm place UV-light transmittance is 90,350nm place UV-light transmittance is the solution of 98, temperature 25 DEG C, pressure 0.8MPa, air speed 5 hours
-1condition under by adsorption bed, adsorb with adsorbent contact, after absorption, the adsorbent solution 220nm place UV-light transmittance obtained is 17,275nm place UV-light transmittance be 92,350nm place UV-light transmittance is 99.
Claims (2)
1. improve a method for quality of glycol, by ethylene glycol raw material, temperature 20 ~ 80 DEG C, pressure 0.1 ~ 2.0MPa, air speed 0.5 ~ 3.0 hour
-1condition under by adsorption bed, with adsorbent contact, after absorption, obtain the effluent of ethylene glycol; It is characterized in that sorbent material adopts at least one in ZSM-5, y-type zeolite or β zeolite, silica alumina ratio is 200 ~ 1000: 1; Wherein ethylene glycol raw material is from hydrogenation of oxalate for preparing ethylene glycol product.
2. improve the method for quality of glycol according to claim 1, it is characterized in that sorbent material adopts ZSM-5 type zeolite, its silica alumina ratio is 300 ~ 800: 1.
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| CN107774008A (en) * | 2016-08-26 | 2018-03-09 | 中国石油化工股份有限公司 | The apparatus and method that a kind of physical absorption improves UV transmittance of ethylene glycol |
| CN113620780A (en) * | 2021-08-06 | 2021-11-09 | 联泓新材料科技股份有限公司 | Method for intermittently preparing polyester-grade ethylene glycol from industrial-grade ethylene glycol |
| CN116253616B (en) * | 2023-05-09 | 2024-01-30 | 南京威尔药业科技有限公司 | Method for removing trace aldehyde in 1, 2-propylene glycol by ultrasonic adsorption |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999058483A1 (en) * | 1998-05-14 | 1999-11-18 | Huntsman Petrochemical Corporation | Improved glycol purification |
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| US6603048B1 (en) * | 1999-10-05 | 2003-08-05 | E. I. Du Pont De Nemours And Company | Process to separate 1,3-propanediol or glycerol, or a mixture thereof from a biological mixture |
| US6770790B1 (en) * | 2003-10-17 | 2004-08-03 | Arco Chemical Technology, L.P. | Purification of tertiary butyl alcohol |
| GB0421928D0 (en) * | 2004-10-01 | 2004-11-03 | Davy Process Techn Ltd | Process |
| CN101928201B (en) * | 2009-06-26 | 2013-04-10 | 上海焦化有限公司 | Purification technique for coal glycol rude products |
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