CN101058526A - Method of increasing quality of glycol - Google Patents
Method of increasing quality of glycol Download PDFInfo
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- CN101058526A CN101058526A CN 200710021425 CN200710021425A CN101058526A CN 101058526 A CN101058526 A CN 101058526A CN 200710021425 CN200710021425 CN 200710021425 CN 200710021425 A CN200710021425 A CN 200710021425A CN 101058526 A CN101058526 A CN 101058526A
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Abstract
The invention discloses an interval or continuous catalytic hydrogenating for ethandiol (weight density at 10-100%), which is characterized by the following: adopting aggregate nickel or palladium carbon as catalyst; transmitting C=C and C-O into saturated material not to adsorbed by ultraviolet in the ethandiol; reducing the content of aldehyde; improving ultraviolet transmission rate; controlling the reacting temperature between 45 deg. c and 95 deg. c; setting the reacting pressure between 0. 05 and 0. 5Mpa and air speed not less than 60h-1; obtaining the product with ultraviolet transmitting rate more than 90% at 220nm, more than 95% at 275nm, more than 99% at 350nm.
Description
Technical field
A kind of method that improves quality of glycol that the present invention relates to, be to utilize metal catalyst with micro organic impurity shortening in the ethylene glycol (massfraction 10%～100%), improve the uv transmittance of ethylene glycol, reduce aldehyde, thereby improve the quality of ethylene glycol.
Background technology
Ethene generates oxyethane with the oxygen reaction under the silver catalyst effect, oxyethane absorbs, resolves and absorb once more laggardly to go into the hydration reactor reaction and generate ethylene glycol and many ethylene glycol through water, reaction solution through multiple-effect evaporation concentrate, rectifying and dewatering, rectifying steam ethylene glycol and many ethylene glycol etc. and separate operation, the ethylene glycol product.The ethylene glycol product that adopts this technology to produce all can reach the purity more than 99.9%, can be used for the production of trevira, but be difficult to express with content owing to exist to some extent in the product, the organic impurity that absorption is arranged in wavelength is 220～350nm scope, this class impurity has influenced the quality product of polyester to some extent, as painted, the intensity of fiber of fiber, color of fiber etc.Therefore, the quality quality of ethylene glycol product depends primarily on ultraviolet permeability value and aldehyde index.
A large amount of studies show that, the impurity that influences the ethylene glycol quality product mainly is some oxidized byproducts that produce inevitably in the oxidising process of ethene, these by products are generally organic oxygen-containing compound, comprise organic compound such as aldehyde, ketone, carboxylic acid, in these impurity, the aldehyde of carboxylic acid compound and band conjugated double bond can occur stronger absorption at the 220nm place as propenal, crotonic aldehyde etc.; And aldehyde, ketone and cyclic diketones compounds can have bigger absorption at the 270nm place.Therefore, reduce the content of this type of impurity, can improve the ethylene glycol product at 220～350nm wavelength region uv transmittance, significant to the quality that improves ethylene glycol.
World patent WO 9958483 and U.S. Pat 3970711 have been introduced the aqueous glycol solution (hydration reaction liquid) that adsorbs lower ethylene glycol of ultraviolet permeability or ethylene oxide hydration reaction generation with gac, the ultraviolet permeability 220nm that makes the ethylene glycol that obtains after the absorption is greater than 76%, 250nm is greater than 90%, and 275nm is greater than 92%.Though charcoal absorption can improve the uv transmittance of ethylene glycol because the loading capacity of acticarbon is very limited, use for some time after effect obviously reduce, and gac is difficult for holomorphosis, the use cost height limits its industrial applications.
U.S. Pat 5770777 and US 6525229 have introduced the treatment process of spent ion exchange resin to the finished product ethylene glycol or ethylene glycol (comprising monoethylene glycol, Diethylene Glycol, the triethylene glycol etc.) aqueous solution, make the ethylene glycol uv transmittance reach exchange and absorption that polyester grade requires resin by ion-exchange, can remove two ketone impurity preferably, improved the ethylene glycol uv transmittance, made the ethylene glycol uv transmittance reach the polyester grade requirement.It is obvious that resin method improves ethylene glycol ultraviolet permeability effect, but, the exchange capacity of ion exchange resin is limited, for extensive ethylene glycol production equipment, not only need a large amount of ion exchange resin, also need often to carry out regeneration of resin, regeneration can produce more acid-base waste fluid, transition intermediate material etc., and this method is unsuitable for the transformation of existing apparatus.
World patent WO 9109828 has introduced the counter osmosis of utilizing semi-permeable membranes, cost-effectively impurity that absorbs UV-light and/or their precursor are separated in the flushing flow of the stripping tower bottom cycle stream from ethylene glycol production, made final ethylene glycol product reach the polyester grade standard.Employed semi-permeable membranes is a kind of composite membrane, is made up of sulfonic acid polysulfones separating layer and polysulfone supporting layer.
U.S. Pat 4358625 has added sodium borohydride in the recycled process water, the aqueous glycol solution that obtains is through separation and purification, and the uv transmittance of ethylene glycol product can improve greatly.
In addition, be reported in addition add alkali in the aqua liquid of oxyethane after, carry out concentrating and separating again, the uv transmittance of ethylene glycol product is improved, more effective to the uv transmittance that improves 220nm.
U.S. Pat 4289593 has proposed a kind ofly to utilize regulatable ultraviolet source that technical grade ethylene glycol is shone, make the compound impurity decomposition and inversion that contains a plurality of pairs of keys that influences uv transmittance in the ethylene glycol and the method that improves the outside line transmitance, the irradiation by high pressure more than wavelength 220nm or low pressure mercury lamp makes the uv transmittance of ethylene glycol reach the standard of fibre-grade.The ultraviolet wavelength of irradiation usefulness must be greater than 220nm, because the irradiation of shorter wavelength can make alcohol generate unwanted aldehyde on the contrary.
U.S. Pat 4647705 discloses and had a kind ofly dripped behind the strong base solution stirring reaction three days in the mixture of ethylene glycol and alumino nickel, handles the method that polyester that the ethylene glycol that obtains can satisfy the producd fibers level requires.But this method is not suitable for large-scale continuous production, and alumino nickel brings inconvenience for the follow-up purification that separates with the aluminum oxide of highly basic reaction generation and excessive alkali.
Summary of the invention
Purpose of the present invention is at the deficiency of existing method, provides that a kind of process implementing is easy, cost is low, to improving the significant method of quality of glycol.With metal catalyst under heating condition to ethylene glycol (mass concentration 10%～100%) intermittently or continuous catalytic hydrogenation, reduce aldehyde wherein, improve its uv transmittance.
Selected metal catalyst is skeleton nickel or palladium carbon, and temperature of reaction is between 45 ℃～95 ℃.Intermittently the catalytic hydrogenation catalyst consumption account for charging capacity 0.5%～2% between; Continuous catalytic hydrogenation employing ethylene glycol enters fixed bed and carries out shortening, reaction pressure 0.05～0.5Mpa, air speed≤60h after hydrogen is delivered to the preheater preheating
-1
The refining EG technical process of successive reaction such as Fig. 1.
Description of drawings
Fig. 1 continuous catalytic hydrogenation is made with extra care the ethylene glycol process flow sheet
Embodiment
Following example will give the present invention and further specifying, but therefore not limit the present invention.
Embodiment 1
Adding 200g left and right sides mass concentration is 85% ethylene glycol in having the 500mL four-hole boiling flask of agitator, thermometer, reflux condensing tube, adds 2mL palladium carbon as catalyzer, and 75 ℃ of control reaction temperature stir, lead to hydrogen 1h.The UV value of material changes as table 1 before and after the hydrogenation.With this hydrogenation material rectification under vacuum, get the ethylene glycol product, measure its uv transmittance and aldehyde, result and not hydrogenation rectifying product comparison are as table 1.
Embodiment 2
As example 1, make catalyzer with Raney's nickel, its consumption is with embodiment 1,70 ℃ of temperature of reaction, the variation of material and ethylene glycol product UV value and aldehyde is as table 1 before and after the hydrogenation.
The main quality index contrast of material and product before and after table 1 hydrogenation
| Rectification under vacuum product behind the hydrogenation | 92.5 | 91.3 | 91.0 | 89.5 | 91.4 | 95.6 | 98.8 | 99.0 | 99.9 | 1.58 |
Embodiment 3
As example 2, quality of glycol concentration is 100%, 95 ℃ of temperature of reaction.Result such as table 2.
The main quality index contrast of material and product before and after table 2 hydrogenation
Embodiment 4
As example 1, make catalyzer with skeleton nickel, quality of glycol concentration is 12.5%, 85 ℃ of temperature of reaction.Result such as table 3.
The main quality index contrast of material and product before and after table 3 hydrogenation
Embodiment 5
Adopting Fig. 1 technical process, in the fixed bed of internal diameter 10mm, long 4cm, is that 85% ethylene glycol is at 65 ℃ of bed temperatures, hydrogen pressure 0.35MPa, air speed 20h with skeleton nickel 2mL filling to mass concentration
-1Shortening under the condition, the ethylene glycol cut is collected in hydrogenation reaction solution rectifying, gets the ethylene glycol product.The uv transmittance and the aldehyde of charging, discharging and ethylene glycol product relatively should see Table 4.
Embodiment 6
As example 5,46 ℃ of bed temperatures, hydrogen pressure 0.15MPa, air speed 30h
-1, the results are shown in Table 4.
The main quality index contrast of material and product before and after table 4 oxygenation
Embodiment 7
As example 5, quality of glycol concentration 12.5%, 80 ℃ of bed temperatures, hydrogen pressure 0.05MPa, air speed 60h
-1, the results are shown in Table 5.
Embodiment 8
As example 5, quality of glycol concentration 12.5%, 53 ℃ of bed temperatures, hydrogen pressure O.5MPa, air speed 35h
-1, the results are shown in Table 5.
The main quality index contrast of material and product before and after table 5 hydrogenation
Claims (3)
1. method that improves quality of glycol, it is characterized in that with skeleton nickel or palladium-carbon catalyst in 45 ℃～95 ℃ scopes of temperature to mass concentration 10%～100% ethylene glycol intermittently or continuous catalytic hydrogenation.
2. a kind of method that improves quality of glycol according to claim 1 is characterized in that intermittently shortening, and catalyst levels accounts for 0.5%～2% of charging capacity.
3. a kind of method that improves quality of glycol according to claim 1 is characterized in that continuous catalytic hydrogenation adopts ethylene glycol to enter fixed-bed catalytic hydrogenation, reaction pressure 0.05～0.5MPa, air speed≤60h after hydrogen is delivered to the preheater preheating
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200710021425 CN101058526A (en) | 2007-04-11 | 2007-04-11 | Method of increasing quality of glycol |
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| CN 200710021425 CN101058526A (en) | 2007-04-11 | 2007-04-11 | Method of increasing quality of glycol |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012113269A1 (en) * | 2011-02-25 | 2012-08-30 | 中国石油化工股份有限公司 | Method for improving quality of ethylene glycol product |
| CN104098439A (en) * | 2013-04-11 | 2014-10-15 | 中国科学院大连化学物理研究所 | Biomass glycol refining method |
| CN104803856A (en) * | 2015-03-31 | 2015-07-29 | 常州大学 | Method for synthesizing benzylamine through continuous catalytic hydrogenation of cyanobenzene |
| CN105658608A (en) * | 2013-10-23 | 2016-06-08 | 巴斯夫欧洲公司 | Method for the preparation of 1,4-butane diol having an apha color index of less than 30 |
| CN105669344A (en) * | 2016-02-29 | 2016-06-15 | 常州大学 | Method for synthesizing cis-pinane by alpha-pinene continuous catalytic hydrogenation |
| EP3450420A4 (en) * | 2016-03-30 | 2020-01-01 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for increasing uv transmittance of ethylene glycol |
| CN112174780A (en) * | 2020-09-27 | 2021-01-05 | 吉化集团油脂化工有限公司 | Control method for improving UV value of ethylene glycol product through low-pressure catalytic hydrogenation |
| CN114436778A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing 1, 4-butanediol by acetal hydrofining |
| CN114456027A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Device and method for preparing styrene through ethylbenzene dehydrogenation |
| WO2023033099A1 (en) * | 2021-09-02 | 2023-03-09 | Ｋｈネオケム株式会社 | Method for producing product 1,3-butylene glycol |
-
2007
- 2007-04-11 CN CN 200710021425 patent/CN101058526A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2012220220B2 (en) * | 2011-02-25 | 2016-08-18 | China Petroleum & Chemical Corporation | Method for improving quality of ethylene glycol product |
| US20130331618A1 (en) * | 2011-02-25 | 2013-12-12 | Shanghai Research Institute Of Petrochemical Technology, Sinopec | Method for improving the quality of ethylene glycol products |
| US9051236B2 (en) | 2011-02-25 | 2015-06-09 | China Petroleum & Chemical Corporation | Method for improving the quality of ethylene glycol products |
| WO2012113269A1 (en) * | 2011-02-25 | 2012-08-30 | 中国石油化工股份有限公司 | Method for improving quality of ethylene glycol product |
| RU2565589C2 (en) * | 2011-02-25 | 2015-10-20 | Чайна Петролеум Энд Кемикал Корпорейшн | Method of improving quality of ethylene glycol products |
| CN104098439A (en) * | 2013-04-11 | 2014-10-15 | 中国科学院大连化学物理研究所 | Biomass glycol refining method |
| CN105658608A (en) * | 2013-10-23 | 2016-06-08 | 巴斯夫欧洲公司 | Method for the preparation of 1,4-butane diol having an apha color index of less than 30 |
| CN105658608B (en) * | 2013-10-23 | 2018-02-23 | 巴斯夫欧洲公司 | Method for preparing 1,4 butanediols of the APHA color indexs less than 30 |
| CN104803856A (en) * | 2015-03-31 | 2015-07-29 | 常州大学 | Method for synthesizing benzylamine through continuous catalytic hydrogenation of cyanobenzene |
| CN105669344A (en) * | 2016-02-29 | 2016-06-15 | 常州大学 | Method for synthesizing cis-pinane by alpha-pinene continuous catalytic hydrogenation |
| EP3450420A4 (en) * | 2016-03-30 | 2020-01-01 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for increasing uv transmittance of ethylene glycol |
| US10836696B2 (en) | 2016-03-30 | 2020-11-17 | The Coca-Cola Company | Method for increasing UV transmittance of ethylene glycol |
| CN112174780A (en) * | 2020-09-27 | 2021-01-05 | 吉化集团油脂化工有限公司 | Control method for improving UV value of ethylene glycol product through low-pressure catalytic hydrogenation |
| CN114456027A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Device and method for preparing styrene through ethylbenzene dehydrogenation |
| CN114436778A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing 1, 4-butanediol by acetal hydrofining |
| WO2023033099A1 (en) * | 2021-09-02 | 2023-03-09 | Ｋｈネオケム株式会社 | Method for producing product 1,3-butylene glycol |
| JPWO2023033099A1 (en) * | 2021-09-02 | 2023-03-09 | ||
| JP7335461B2 (en) | 2021-09-02 | 2023-08-29 | Ｋｈネオケム株式会社 | Manufacturing method of product 1,3-butylene glycol |
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Open date: 20071024 |