CN102276418A - Ethylene glycol purification method - Google Patents
Ethylene glycol purification method Download PDFInfo
- Publication number
- CN102276418A CN102276418A CN2010102000385A CN201010200038A CN102276418A CN 102276418 A CN102276418 A CN 102276418A CN 2010102000385 A CN2010102000385 A CN 2010102000385A CN 201010200038 A CN201010200038 A CN 201010200038A CN 102276418 A CN102276418 A CN 102276418A
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- butyleneglycol
- purifying
- weight content
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an ethylene glycol purification method for mainly solving the technical problem of difficulty in separating ethylene glycol and butanediol and low purity of the ethylene glycol in the prior art. In a technical scheme adopted in the invention, a mixture liquid containing ethylene glycol and 1,2-butanediol comes into contact with an adsorbent through an adsorbent bed under the conditions of the temperature of 10-100 DEG C, the pressure of 0.1-3.0Mpa and the air speed of 0.2-5.9 h<-1>, and effluent rich in the ethylene glycol is obtained after adsorption, wherein the adsorbent is selected from at least one of ZSM-5, Y-type zeolite and beta zeolite, and the molar ratio of silicon to aluminum is (200-1000):1. Accordingly, the problems are solved favorably by means of the technical scheme. The ethylene glycol purification method can be used in industrial production for ethylene glycol purification.
Description
Technical field
The present invention relates to a kind of method of ethylene glycol purifying, particularly about the method for ethylene glycol purifying in the product of dimethyl oxalate hydrogenation or oxalic acid diethyl ester hydrogenation preparing ethylene glycol.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, be mainly used in and produce trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used for industries such as coating, soup, brake fluid and printing ink in addition, solvent and medium as ammonium pertorate, be used to produce special solvent glycol ether etc., purposes is very extensive.
At present, direct hydration method or the legal operational path of pressurized water are all adopted in domestic and international large-scale ethylene glycol production, this technology is that oxyethane and water are made into mixed aqueous solution by 1: 20～22 (mol ratios), in fixed-bed reactor in 130～180 ℃, 1.0～2.5MPa reacted 18～30 minutes down, oxyethane all is converted into alcohol mixture, the aqueous glycol solution content that generates is greatly about 10% (massfraction), carry through the multiple-effect evaporator dehydration then and obtain ethylene glycol dense the separation with rectification under vacuum, but production equipment need be provided with a plurality of vaporizers, consume lot of energy and be used for dehydration, cause the technological process of production long, equipment is many, the energy consumption height, directly influence the production cost of ethylene glycol.Since the seventies in 20th century, both at home and abroad some major companies that mainly produce ethylene glycol all are devoted to the Synthesis of Ethylene Glycol by Catalytic Hydration Study on Technology, mainly contain shell company, U.S. UCC company and Dow company, the Mitsubishi chemical company of Ying He, domestic Shanghai Petroleum Chemical Engineering Institute, Nanjing University of Technology etc.What representative was wherein arranged is the heterogeneous catalysis hydration method of Shell company and the homogeneous catalysis hydration method of UCC company.Shell company has reported that from 1994 quaternary ammonium type acid carbonate anionite-exchange resin carries out the exploitation of EO catalytic hydration technology as catalyzer, obtain EO transformation efficiency 96%～98%, the test-results of EG selectivity 97%～98%, develop the poly organic silicon alkane ammonium salt loaded catalyst of similar silicon dioxide skeleton and the epoxide hydrating process under the catalysis thereof in 1997 again, obtained better conversion rate and selectivity.The UCC company of the U.S. has mainly developed two kinds of hydration catalysts: a kind of is the anionic catalyst that is carried on the ion exchange resin, mainly is molybdate, tungstate, vanadate and triphenylphosphine complex catalyst; Another kind is the molybdate composite catalyst.In two kinds of Application of Catalyst examples, the TM catalyzer of spent ion exchange resin DOWEXWSA21 preparation is hydration under 9: 1 the condition in the mol ratio of water and EO, and the EG yield is 96%.Using the molybdate composite catalyst, is hydration under 5: 1 the condition in the mol ratio of water and EO, and the EG yield is 96.6%.Catalysis method greatly reduces the water ratio, simultaneously can obtain high EO transformation efficiency and high EG selectivity, but also there is certain problem aspect Preparation of Catalyst, regeneration and life-span, not enough as catalyst stability, preparation is quite complicated, be difficult to recycle, have also can be in product residual a certain amount of anionic metal, need to increase corresponding apparatus and separate.NSC 11801 method synthesizing glycol is by oxyethane and carbonic acid gas synthesizing ethylene carbonate, obtains ethylene glycol with the NSC 11801 hydrolysis again.The US4508927 patent proposes esterification and hydrolysis reaction are separately carried out.The two-step process that the US4500559 of U.S. Halcon-SD company proposes is that the mixture that comes from reactor is through resorber, again with the carbonic acid gas extracting oxyethane under the criticality, obtain oxyethane, carbonic acid gas, water mixture contacts synthetic BC with catalyst for esterification reaction such as Organohalogen compounds, sulfohalides, BC is admitted to hydrolysis reactor then, and hydrolysis obtains ethylene glycol and carbonic acid gas under same catalyst action, and the ethylene glycol yield is up to 99%.Japanese Patent JP571006631 has proposed the EO-EC-EG novel process of industrially scalable, patent introduces oxyethane and the carbonic acid gas esterification is in the presence of catalyzer KI, 160 ℃ are carried out esterification, transformation efficiency is 99.9%, the selectivity of ethylene glycol is 100%, the NSC 11801 legal system is equipped with the ethylene glycol technology no matter aspect transformation efficiency and selectivity, still all than present BO direct hydration method bigger advantage is being arranged aspect production process raw material consumption and the energy expenditure, technical in ethylene glycol is a kind of method that maintains the leading position.But this method still is raw material with the oil, and need build the ethylene glycol production equipment again, and this glycol unit to new construction is more suitable, and on original production unit was undergone technological transformation, it was favourable to be not so good as catalytic hydration.
Document CN101138725A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and it is active ingredient with the metallic copper, and zinc is auxiliary agent, adopts the coprecipitation method preparation.Document " petrochemical complex " was rolled up the 340th～343 page of the 4th phase in 2007 the 36th and has been introduced a kind of employing Cu/SiO
2Carry out the research of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol reaction.Above-mentioned document is not all mentioned the issues of purification of ethylene glycol.
At present, from world wide, petroleum resources day is becoming tight, and oil price fluctuation in the world's is bigger, 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.With the carbon monoxide is the feedstock production barkite, is a very attractive Coal Chemical Industry route then with preparing glycol by hydrogenating oxalate.Now both at home and abroad to being that the research of feedstock production barkite has obtained good effect with the carbon monoxide, industrial production is ripe.And, still have more need of work further investigation with preparing glycol by hydrogenating oxalate, especially how to obtain highly purified ethylene glycol, and then ensure that the quality of product is an important topic.And there is not disclosed bibliographical information at present.
Summary of the invention
Technical problem to be solved by this invention is ethylene glycol that exists in the conventional art and the technical problem that the butyleneglycol difficulty is separated and ethylene glycol purity is low, and a kind of method of new ethylene glycol purifying is provided.This method has ethylene glycol purity 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 of ethylene glycol purifying, will contain ethylene glycol and 1, and the mixed solution of 2-butyleneglycol, 10～100 ℃ of temperature, pressure 0.1～3.0MPa, air speed 0.2～5.0 hour
-1Condition under by adsorption bed, contact with sorbent material, obtain being rich in the effluent of ethylene glycol after the absorption; It is at least a to it is characterized in that sorbent material adopts in ZSM-5, y-type zeolite or the β zeolite, and silica alumina ratio is 200～1000: 1.
Sorbent material is preferably from ZSM-5 type zeolite in the technique scheme, and the silica alumina ratio preferable range is 300～800: 1.The preferred operations condition of adsorption bed is: 20～80 ℃ of temperature, pressure 0.1～2.0MPa, air speed 0.5～3.0 hour
-1Ethylene glycol and 1, in the mixed solution of 2-butyleneglycol 1, the content preferable range of 2-butyleneglycol is greater than zero～30%, ethylene glycol and 1, in the mixed solution of 2-butyleneglycol 1, the content of 2-butyleneglycol more preferably scope is greater than zero～20%, and most preferred range be greater than zero～10%.
Ethylene glycol and 1 in the technique scheme, the mixed solution of 2-butyleneglycol is from the hydrogenation of oxalate for preparing ethylene glycol product.
As everyone knows, in the hydrogenation of oxalate for preparing ethylene glycol reaction process, except the ethylene glycol target product, also contain a certain amount of by product, as ethanol, butyleneglycol and propylene glycol etc., and ethylene glycol and 1, the boiling point of 2-butyleneglycol is close, adopts conventional method to be difficult to separate, thereby influences the quality and the use of product.
The discovery that the present inventor is surprised under study for action, adopting ZSM-5, y-type zeolite or β zeolite is sorbent material, to ethylene glycol and 1,1 in the 2-butyleneglycol, the 2-butyleneglycol has higher adsorption selectivity, and especially the ZSM-5 zeolite is better.The inventive method, fractionation by adsorption efficient height, and also technology is simple, is easy to accomplish scale production.
Adopt technical scheme of the present invention, with 1, the content of 2-butyleneglycol is the ethylene glycol and 1 greater than zero～30%, and the mixed solution of 2-butyleneglycol is a raw material, and adopting MFI type zeolite is sorbent material, 10～100 ℃ of temperature, and pressure 0.1～3.0MPa, air speed 0.2～5.0 hour
-1Condition under by adsorption bed, contact with sorbent material, the purity of the ethylene glycol that obtains after the absorption has obtained better technical effect greater than 99.8%.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1～9]
Filling 300 gram ZSM-5 type zeolite (its silica alumina ratio is 600: 1) sorbent materials feed ethylene glycol weight content 90%, 1 in adsorption bed, the solution of 2-butyleneglycol weight content 10%, under the condition shown in the following table, adsorb, adsorb saturated after, the result who obtains is as follows:
Table 1
| Sequence number | Temperature ℃ | Air speed hour -1 | Pressure MPa | The weight content of ethylene glycol, % | 1, the weight content of 2-butyleneglycol, % |
| 1 | 20 | 0.22 | 1.0 | 99.91 | 0.09 |
| 2 | 30 | 0.45 | 0.5 | 99.88 | 0.12 |
| 3 | 50 | 0.67 | 5.0 | 99.8 | 0.2 |
| 4 | 80 | 0.83 | 3.5 | 99.72 | 0.28 |
| 5 | 30 | 1.8 | 0.5 | 99.68 | 0.32 |
| 6 | 50 | 1.2 | 2.5 | 99.66 | 0.34 |
| 7 | 60 | 2.5 | 0.1 | 99.82 | 0.18 |
| 8 | 40 | 0.63 | 2.0 | 99.81 | 0.19 |
| 9 | 50 | 0.44 | 1.5 | 99.76 | 0.24 |
[embodiment 10～18]
Filling 300 gram ZSM-5 type zeolite ((its silica alumina ratio is 350: 1)) sorbent materials feed the absorption raw material shown in the following table in adsorption bed, 50 ℃ of temperature, and pressure 0.5MPa, air speed 0.5 hour
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the result who obtains is as shown in the table:
Table 2
| Sequence number | The weight content of ethylene glycol in the raw material, % | In the raw material 1, the weight content of 2-butyleneglycol, % | The weight content of absorption back ethylene glycol, % | Absorption back 1, the weight content of 2-butyleneglycol, % |
| 10 | 80 | 20 | 99.51 | 0.49 |
| 11 | 70 | 30 | 99.43 | 0.57 |
| 12 | 90 | 10 | 99.63 | 0.37 |
| 13 | 95 | 5 | 99.8 | 0.2 |
| 14 | 98 | 2 | 99.86 | 0.14 |
| 15 | 99 | 1 | 99.91 | 0.09 |
| 16 | 99.5 | 0.5 | 99.97 | 0.03 |
| 17 | 85 | 15 | 99.58 | 0.42 |
| 18 | 88 | 12 | 99.61 | 0.39 |
[embodiment 19]
Filling 500 gram ZSM-5 type zeolite (its silica alumina ratio is 800: 1) sorbent materials feed ethylene glycol weight content 94%, 1 in adsorption bed, the absorption raw material of 2-butyleneglycol weight content 6%, and 20 ℃ of temperature, pressure 2.8MPa, air speed 4.8 hours
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the adsorbent solution that obtains is: ethylene glycol weight content 99.92%, 1,2-butyleneglycol weight content 0.08%.
[embodiment 20]
Filling 500 gram ZSM-5 type zeolite (its silica alumina ratio is 450: 1) sorbent materials feed ethylene glycol weight content 97% in adsorption bed, the absorption raw material of methylcarbonate weight content 3%, and 90 ℃ of temperature, pressure 2.0MPa, air speed 3.5 hours
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the adsorbent solution that obtains is: ethylene glycol weight content 99.86%, 1,2-butyleneglycol weight content 0.14%.
[embodiment 21]
Filling 500 gram y-type zeolite ((its silica alumina ratio is 200: 1)) sorbent materials feed ethylene glycol weight content 96%, 1 in adsorption bed, the absorption raw material of 2-butyleneglycol weight content 4%, and 70 ℃ of temperature, pressure 1.5MPa, air speed 1.5 hours
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the adsorbent solution that obtains is: ethylene glycol weight content 99.80%, 1,2-butyleneglycol weight content 0.20%.
[embodiment 22]
Filling 500 gram zeolite beta ((its silica alumina ratio is 260: 1)) sorbent materials feed ethylene glycol weight content 98%, 1 in adsorption bed, the absorption raw material of 2-butyleneglycol weight content 2%, and 50 ℃ of temperature, pressure 0.8MPa, air speed 0.5 hour
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the adsorbent solution that obtains is: ethylene glycol weight content 99.88%, 1,2-butyleneglycol weight content 0.12%.
[comparative example 1]
Each step and operational condition according to embodiment 1, just adopt the conventional rectification tower to separate, 70 of theoretical column plates, reflux ratio 10: 1,140 ℃ of tower still temperature, absolute pressure are under the condition of 20KPa, the cat head discharging, glycol content is 90%, and ethylene glycol is with respect to 1, and the 2-butyleneglycol is not purified.
Claims (7)
1. the method for an ethylene glycol purifying will contain ethylene glycol and 1, the mixed solution of 2-butyleneglycol, and 10～100 ℃ of temperature, pressure 0.1～3.0MPa, air speed 0.2～5.0 hour
-1Condition under by adsorption bed, contact with sorbent material, obtain being rich in the effluent of ethylene glycol after the absorption; It is at least a to it is characterized in that sorbent material adopts in ZSM-5, y-type zeolite or the β zeolite, and silica alumina ratio is 200～1000: 1.
2. according to the method for the described ethylene glycol purifying of claim 1, it is characterized in that sorbent material adopts ZSM-5 type zeolite, its silica alumina ratio is 300～800: 1.
3. according to the method for the described ethylene glycol purifying of claim 1, it is characterized in that 20～80 ℃ of the temperature of adsorption bed, pressure 0.1～2.0MPa, air speed 0.5～3.0 hour
-1
4. according to the method for the described ethylene glycol purifying of claim 1, it is characterized in that ethylene glycol and 1, in the mixed solution of 2-butyleneglycol 1, the content of 2-butyleneglycol is greater than zero～30%.
5. according to the method for the described ethylene glycol purifying of claim 4, it is characterized in that ethylene glycol and 1, in the mixed solution of 2-butyleneglycol 1, the content of 2-butyleneglycol is greater than zero～20%.
6. according to the method for the described ethylene glycol purifying of claim 5, it is characterized in that ethylene glycol and 1, in the mixed solution of 2-butyleneglycol 1, the content of 2-butyleneglycol is greater than zero～10%.
7. according to the method for the described ethylene glycol purifying of claim 1, it is characterized in that ethylene glycol and 1, the mixed solution of 2-butyleneglycol is from the hydrogenation of oxalate for preparing ethylene glycol product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102000385A CN102276418B (en) | 2010-06-11 | 2010-06-11 | Ethylene glycol purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102000385A CN102276418B (en) | 2010-06-11 | 2010-06-11 | Ethylene glycol purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102276418A true CN102276418A (en) | 2011-12-14 |
| CN102276418B CN102276418B (en) | 2013-07-31 |
Family
ID=45102211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102000385A Active CN102276418B (en) | 2010-06-11 | 2010-06-11 | Ethylene glycol purification method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102276418B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372598A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for separating glycol from butanediol |
| CN114057547A (en) * | 2020-08-03 | 2022-02-18 | 长春美禾科技发展有限公司 | Refining method of bio-based crude ethylene glycol |
| CN115337671A (en) * | 2022-07-14 | 2022-11-15 | 陕西榆能化学材料有限公司 | Method for improving quality of coal-to-ethylene glycol product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966658A (en) * | 1989-12-27 | 1990-10-30 | Lloyd Berg | Recovery of ethylene glycol from butanediol isomers by azeotropic distillation |
| CN1580020A (en) * | 2003-08-05 | 2005-02-16 | 中国石化上海石油化工股份有限公司 | Etharediol refined purifying method |
-
2010
- 2010-06-11 CN CN2010102000385A patent/CN102276418B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966658A (en) * | 1989-12-27 | 1990-10-30 | Lloyd Berg | Recovery of ethylene glycol from butanediol isomers by azeotropic distillation |
| CN1580020A (en) * | 2003-08-05 | 2005-02-16 | 中国石化上海石油化工股份有限公司 | Etharediol refined purifying method |
Non-Patent Citations (1)
| Title |
|---|
| 郭照冰等: "MFI型沸石吸附分离水体中混合硝基氯苯的研究", 《环境科学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372598A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for separating glycol from butanediol |
| CN114057547A (en) * | 2020-08-03 | 2022-02-18 | 长春美禾科技发展有限公司 | Refining method of bio-based crude ethylene glycol |
| CN115337671A (en) * | 2022-07-14 | 2022-11-15 | 陕西榆能化学材料有限公司 | Method for improving quality of coal-to-ethylene glycol product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102276418B (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475441B (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN101475442B (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN102372596B (en) | Method for producing glycol product by separating synthetic gas | |
| CN101475443B (en) | Method for preparing ethylene glycol | |
| CN101993344B (en) | Method for preparing ethylene glycol from synthesis gas | |
| CN102372600B (en) | Separation method for glycol, propylene glycol and butylene glycol | |
| CN102649704B (en) | Method for purifying ethylene glycol product | |
| CN102219641B (en) | Method for purifying ethylene glycol | |
| CN102372597A (en) | Method for separating glycol product produced from syngas | |
| CN102219640A (en) | Method for improving selectivity for making glycol by adding hydrogen in oxalate | |
| CN102276418B (en) | Ethylene glycol purification method | |
| CN102372599B (en) | Method for separating glycol and butylene glycol | |
| CN102372598A (en) | Method for separating glycol from butanediol | |
| CN101993343B (en) | Multi-stage synthesis method of ethylene glycol | |
| CN101993345A (en) | Method for improving selectivity of glycol prepared by adding hydrogen into oxalate | |
| CN102372601B (en) | Method for separating ethylene glycol, propanediol and butanediol | |
| CN102219639B (en) | Method for preparing glycol by virtue of hydrogenation of oxalate | |
| CN102649686A (en) | Method for synthesizing ethylene glycol | |
| CN101993365A (en) | Method for producing oxalic ester by CO coupling | |
| CN101993341B (en) | Method for producing glycol through hydrogenation of oxalic ester | |
| CN102649691B (en) | Method for improving selectivity of ethylene glycol prepared through hydrogenation reaction by oxalic ester | |
| CN102649689B (en) | Method for parking reactor | |
| CN102649701B (en) | Method for stopping reactor in hydrogenation of oxalate to ethylene glycol | |
| CN101993342A (en) | Method for preparing glycol by using oxalic ester | |
| CN114432724B (en) | Process system and method for isopropanol dehydration reaction and process system and method for preparing propylene from acetone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |