CN1065656A - The preparation of diglycol monotertiary butyl ether - Google Patents
The preparation of diglycol monotertiary butyl ether Download PDFInfo
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- CN1065656A CN1065656A CN 91102158 CN91102158A CN1065656A CN 1065656 A CN1065656 A CN 1065656A CN 91102158 CN91102158 CN 91102158 CN 91102158 A CN91102158 A CN 91102158A CN 1065656 A CN1065656 A CN 1065656A
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Abstract
The preparation method of a kind of diglycol monotertiary butyl ether (MBE) is glycol ether and cracking C
4Cut divinyl raffinate is made catalyzer as super beginning raw material with macroporous strong-acid cation-exchange resin, 40～85 ℃ of temperature, and pressure 1.0～3.0MPa (table), alfin mol ratio 1.0～3.0 is during liquid feeding air speed 0.5-3.0
-1, under linear speed 180-350 centimetre/hour the condition, react generation MBE by fixed-bed reactor continuously.Isobutene conversion is 80～85%, and the MBE selectivity is 90～97%.Because raw material sources are abundant, and are cheap, can reduce production costs significantly.
Description
The present invention is the preparation method of a kind of diglycol monotertiary butyl ether (MBE)
Therefore its dissolving power is strong because of containing ether and hydroxyl for the glycol ether ether material, and smell is little, is suitable for the fine solvent of low toxicity or micro-virus kind, is widely used in coating, printing-ink, metal cleaner, family's liquid ceanser and brake fluid, industries such as wood preservative.
Usually the glycol ether ether material all is to do raw material with oxyethane and corresponding alcohols, prepares by addition reaction.[" utilization of Diethylene Glycol in fine chemistry industry " (main office of China Petrochemical Industry is fine chemistry industry proceedings for the first time), Ж y Р Н А Л А Н А Л И Т И Ч Е С К О Й Х И М И И 37(8) 1505-10] and MBE is to be raw material with the trimethyl carbinol and oxyethane, alcohol is received the etherification method preparation of making catalyzer.170～220 ℃ of temperature of reaction, reaction pressure 1.0～2.0MPa generates the glycol monomethyl tertbutyl ether successively, diglycol monotertiary butyl ether (MBE), triglycol list tertbutyl ether.Suitably the ratio of the regulating ring oxidative ethane and the trimethyl carbinol can make MBE become principal product, yet this method exists oxyethane and trimethyl carbinol cost of material expensive, manufacturing cost height, and shortcoming such as by product is many, and selectivity is low.
The another kind of method of synthetic MBE is glycol ether and the etherification reaction of iso-butylene under the inorganic acid catalyst effect, and this method is present in the many and equipment corrosion problem of by product.And be raw material with ethylene glycol and iso-butylene, synthesizing glycol list tertbutyl ether has but had progress under the effect of storng-acid cation exchange resin.（EP-0035075;EP-001，651;EP0，003，128;US4299，997）
To make catalyzer of storng-acid cation exchange resin the etherificate of ethylene glycol and iso-butylene was done research in above-mentioned US and European patent, but its objective is for synthesizing glycol list tertbutyl ether, though the etherificate to MBE is also mentioned, and does not do systematic study, there is not industrial application yet.
The objective of the invention is to set up a kind of employing glycol ether and cracking C
4Novel process for the synthetic MBE of raw material.This technological reaction condition relaxes, and side reaction is few, and flexibility of operation is big, applicable to the C of different iso-butylene content
4Raw material can change the product ratio of single, double ether flexibly by adjusting process, and by add less water in raw material, this technology can become and produce the technology of the MBE and the trimethyl carbinol.Thereby solve problems such as MBE production cost height and equipment corrosion and selectivity are low.Simultaneously, utilize technology of the present invention, can make glycol ether and C
4Two kinds of petrochemical by-products of fraction obtain reasonable use.
Preparation technology's schema that etherification technology provided by the invention can contrast Fig. 1 MBE is illustrated.It is with glycol ether (II) and contains the C of iso-butylene
4Fraction (I), is heated to certain temperature through heat exchanger (9) and enters reactor (1) after the circulation glycol ether mixes as raw material, and reaction product adds less water (III) and reclaim unreacted C in distillation tower (2)
4Fraction (IV), tower (2) still liquid enter tower (3) and carry out component distillation, and the azeotrope that cat head steams water, glycol ether dual-tert-butyl ether (DBE) and (MBE) forms after heat exchanger (8) cooling, is divided into the profit two-phase in liquid-liquid separation groove (7).The water total reflux, the oil phase of the two butyl ethers (DBE) of rich glycol ether is sent into distillation tower (4) and is steamed the mixture that thing is water and a small amount of glycol ether dual-tert-butyl ether and MBE, return liquid-liquid separation Cao (7), the tower still then arrives highly purified glycol ether dual-tert-butyl ether (V) (DBE).The still liquid of tower (3) is mainly diglycol monotertiary butyl ether (MBE) and glycol ether, and it is imported distillation tower (5), overhead product be highly purified diglycol monotertiary butyl ether (VI) (MBE).Bottoms is a glycol ether, imports simple distillation tower (6), removes metallic impurity after the gasification, recycles then.Tower still row raffinate (VII).
Dress Hydrogen macropore strong acid cation exchange resin in the reactor (1).At reaction pressure 1.0～3.0MPa, 40～85 ℃ of temperature of reaction, volume space velocity 2.0～3.0 o'clock
-1, finish etherification reaction under 240～350 centimetres of/hour conditions of liquid linear speed.
Etherification technology of the present invention has more following characteristics:
(1) reaction conditions relaxes, and thick product separation is refining simple, applicable to the C of different iso-butylene content
4Raw material.
(2) the MBE product of production different purity as required.
(3) can be convenient by the adjusting process condition, change single, double ether product ratio neatly.
(4) main process adopts continuous processing production, device separate unit throughput height.
Following example is with the implementation method that further specifies.
Example 1
By the testing apparatus of Fig. 1, glycol ether and the C that contains iso-butylene
4Fraction adds reactor (1), and this reactor is the stainless steel reaction pipe of 1.2 centimetres of internal diameters, interior filling 120ml large porous strong acid cation exchange resin, reaction conditions: 60 ℃ of temperature, pressure 2.0MPa, glycol ether inlet amount 174ml/ hour, C
4Fraction (iso-butylene content 46%(V
T)), inlet amount 186ml/ hour, promptly the alfin mol ratio 2.0, during volume space velocity 3.0
-1, 360 centimetres/hour of liquid feeding linear speeds.Resultant of reaction is through gas chromatographic analysis, gently change rate of iso-butylene 83.6%
Diglycol monotertiary butyl ether selectivity 93.1%
Glycol ether dual-tert-butyl ether selectivity 6.9%
Example 2
In being 1.2 centimetres stainless steel reaction pipe, the internal diameter identical with example 1 load 50
*Resin 60ml, reaction conditions, 60 ℃ of temperature, pressure 2.0MPa, C
493 milliliters/hour of fraction inlet amounies, 87 milliliters/hour of glycol ether inlet amounies, promptly the alfin mol ratio 2.0, during liquid space-time 3.0
-1, the liquid feeding linear speed is 180 centimetres/hour.
Resultant of reaction is through gc analysis, isobutene conversion 77.1%, diglycol monotertiary butyl ether selectivity 84.8%, glycol ether dual-tert-butyl ether selectivity 15.2%.
Example 3
By the experimental installation of Fig. 1, raw material and catalyzer be with example 1, reaction conditions: pressure 2.0MPa, and during air speed 2.0
-1, 240 centimetres/hour of linear speeds, the alfin mol ratio is as shown in table 1 to the influence of etherification reaction.
Example 4
By the experimental installation of Fig. 1, raw material and catalyzer are with example 1, and reaction conditions: pressure 2.0MPa, alfin mol ratio 2.0 is during air speed 2.0
-1, 240 centimetres/hour of linear speeds.
Temperature is as shown in table 2 to the influence of etherification reaction.
Example 5
By the testing apparatus of Fig. 1, raw material and catalyzer be with example 1, reaction conditions: 50 ℃ of temperature, and during air speed 2.0
-1, alfin mol ratio 2.0,240 centimetres/hour of linear speeds.
Pressure is as shown in table 3 to the influence of etherification reaction.
Example 6
By the testing apparatus of Fig. 1, raw material and catalyzer be with example 1, reaction conditions: 60 ℃ of temperature, pressure 2.0MPa, alfin mol ratio 2.0.
Air speed is as shown in table 4 to the influence of etherification reaction.
Example 7
By the testing apparatus of Fig. 1, raw material and catalyzer be with example 1, reaction conditions: 60 ℃ of temperature, pressure 2.0MPa, alfin mol ratio 2.0.
The reaction mass linear speed is as shown in table 5 to the influence of etherification reaction.
Table 1, alfin mol ratio are to the influence of etherification reaction
Alfin ratio isobutene conversion % glycol ether transformation efficiency % MBE selectivity % MBE yield %
1.1 78.1 60.1 75.3 59.2
1.7 82.2 45.0 87.7 72.1
2.0 83.2 33.8 90.4 75.2
2.7 85.3 30.5 90.7 77.3
3.2 86.5 25.3 91.7 79.3
Reaction conditions:
Pressure: 2.0MPa alfin mol ratio: 2.0
Air speed: 2.0 o'clock
-1Linear speed: 240 centimetres/hour
Table 2, temperature are to the influence of etherification reaction
Temperature of reaction ℃ isobutene conversion % MBE selectivity % MBE yield % DBE selectivity %
40 51.6 98.1 50.6 1.9
50 82.4 95.6 73.9 4.4
60 85.2 91.7 78.1 8.3
70 86.9 73.2 67.9 20.3
Reaction conditions:
Pressure: 2.0MPa alfin ratio: 2.0
Air speed: 2.0 o'clock
-1Linear speed: 240 centimetres/hour
Table 3, pressure are to the influence of etherification reaction
Pressure MPa isobutene conversion % DEG transformation efficiency % MBE selectivity % DBE selectivity %
1.0 82.7 39.6 96 4.0
2.0 82.4 39.9 95.6 4.4
3.0 82.9 40.6 96.0 4.0
Reaction conditions:
Temperature: 50 ℃ of alfin mol ratios: 2.0
Air speed: 2.0 o'clock
-1Linear speed: 240 centimetres/hour
Table 4, air speed are to the influence of etherification reaction
During air speed
-1Isobutene conversion % MBE selectivity % MBE yield %
1.0 89.6 66.0 59.1
1.5 87.4 86.2 75.4
2.0 85.5 91.7 78.4
3.0 83.6 93.1 77.8
Reaction conditions:
Temperature: 50 ℃ of pressure: 2.0MPa
Alfin mol ratio: 2.0
Table 5, material linear speed are to the influence of etherification reaction
Reaction conditions:
Temperature: 60 ℃ of pressure: 2.0MPa
Alfin mol ratio: 2.0
Claims (11)
1, the preparation method of a kind of diglycol monotertiary butyl ether (MBE) with strongly acidic cation-exchange fat catalyzer, is characterized in that the preparation method is: with glycol ether (DEG) and the C that contains iso-butylene
4Fraction is a raw material, continuously by being the fixed-bed reactor of catalyzer with the strongly acidic cation-exchange, and 40～85 ℃ of temperature, pressure 1.0～3.0MPa, the alfin mol ratio is 1.0～3.2 in the raw material, during volume space velocity 0.5-3
-1, synthetic MBE under the etherification conditions that linear speed is 180～360 centimetres/hour.
2, the method for claim 1 is characterized in that described temperature of reaction is 50～70 ℃.
3, the method for claim 1 is characterized in that described reaction pressure is 1～2MPa(gauge pressure).
4, the method for claim 1 is characterized in that glycol ether and C
4The mol ratio of middle iso-butylene is 1.8～3.0.
5, the method for claim 1, the liquid hourly space velocity that it is characterized in that reactant are 1～3 o'clock
-1
6,, it is characterized in that linear speed is 240-360 centimetre/hour as claim 1 and the described method of claim 5.
7, the method for claim 1 is characterized in that water alkene mol ratio is 0～0.2.
8, the method for claim 1 is characterized in that containing the C of iso-butylene
4Fraction is the divinyl raffinate.
9, the method for claim 1 is characterized in that used storng-acid cation exchange resin is the Hydrogen macroporous strong-acid cation-exchange resin.
10, the method for claim 1 is characterized in that described reactor is fixed-bed reactor.
11, the method for claim 1 is characterized in that the reaction product employing adds the water component distillation and isolates product and by product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102158 CN1065656A (en) | 1991-04-09 | 1991-04-09 | The preparation of diglycol monotertiary butyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102158 CN1065656A (en) | 1991-04-09 | 1991-04-09 | The preparation of diglycol monotertiary butyl ether |
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|---|---|
| CN1065656A true CN1065656A (en) | 1992-10-28 |
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|---|---|---|---|
| CN 91102158 Pending CN1065656A (en) | 1991-04-09 | 1991-04-09 | The preparation of diglycol monotertiary butyl ether |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8766015B2 (en) | 2011-02-22 | 2014-07-01 | Daelim Industrial Co., Ltd. | Method for preparing a glycol mono-tertiary-butylether compound |
| CN105061160A (en) * | 2015-07-22 | 2015-11-18 | 珠海飞扬新材料股份有限公司 | Diol tertiary butyl ether production method |
| CN106397137A (en) * | 2015-07-27 | 2017-02-15 | 万华化学集团股份有限公司 | Method for preparing diol mono-tert-butyl ether |
| CN113461496A (en) * | 2020-03-30 | 2021-10-01 | 中国石油化工股份有限公司 | Synthesis method and synthesis system of dihydric alcohol mono-tert-butyl ether |
| CN114456047A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Process for producing low-polymerized tertiary alkyl ether |
-
1991
- 1991-04-09 CN CN 91102158 patent/CN1065656A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8766015B2 (en) | 2011-02-22 | 2014-07-01 | Daelim Industrial Co., Ltd. | Method for preparing a glycol mono-tertiary-butylether compound |
| CN105061160A (en) * | 2015-07-22 | 2015-11-18 | 珠海飞扬新材料股份有限公司 | Diol tertiary butyl ether production method |
| CN106397137A (en) * | 2015-07-27 | 2017-02-15 | 万华化学集团股份有限公司 | Method for preparing diol mono-tert-butyl ether |
| CN106397137B (en) * | 2015-07-27 | 2019-04-23 | 万华化学集团股份有限公司 | A method of preparing glycol ChanShuDing ether |
| CN113461496A (en) * | 2020-03-30 | 2021-10-01 | 中国石油化工股份有限公司 | Synthesis method and synthesis system of dihydric alcohol mono-tert-butyl ether |
| CN114456047A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Process for producing low-polymerized tertiary alkyl ether |
| CN114456047B (en) * | 2020-10-22 | 2024-05-17 | 中国石油化工股份有限公司 | Process for producing oligomeric tertiary alkyl ether |
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