METHOD FOR PREPARING DOUBLE-SEALED-END GLYCOL ETHER

Abstract

Disclosed is a method for preparing a double end capped glycol ether, the method comprising: introducing into a reactor a raw material comprising a glycol monoether and a monohydric alcohol ether, and enabling the raw material to contact and react with an acidic molecular sieve catalyst to generate a double end capped glycol ether, a reaction temperature being 50-300° C., a reaction pressure being 0.1-15 MPa, a WHSV of the glycol monoether in the raw material being 0.01-15.0 h.sup.−1, and a mole ratio of the monohydric alcohol ether to the glycol monoether in the raw material being 1-100:1. The method of the present invention enables a long single-pass lifespan of the catalyst and repeated regeneration, has a high yield and selectivity of a target product, low energy consumption during separation of the product, a high economic value of a by-product, and is flexible in production scale and application.

Claims

1. A method for preparing a double end-capped ethylene glycol ether, in which a raw material containing an ethylene glycol monoether and a monohydric alcohol ether is introduced into a reactor, contacting with a catalyst containing an acidic molecular sieve and reacting to produce the double end-capped ethylene glycol ether; wherein, the reaction temperature is in a range from 50° C. to 300° C., and the reaction pressure is in a range from 0.1 Mpa to 15 Mpa; the weight hourly space velocity of the ethylene glycol monoether in the raw material is in a range from 0.01 h.sup.−1 to 15.0 h.sup.−1; and the molar ratio of the monohydric alcohol ether to the ethylene glycol monoether in the raw material is that monohydric alcohol ether:ethylene glycol monoether is in a range from 1:1 to 100:1.

2. The method according to claim 1, wherein the ethylene glycol monoether is at least one selected from the group consisting of compounds with the structure represented by Formula I:
R.sup.1—O—CH.sub.2—CH.sub.2—OH  Formula I; the monohydric alcohol ether is at least one selected from the group consisting of compounds with the structure represented by Formula II:
R.sup.2—O—R.sup.2  Formula II; the double end-capped ethylene glycol ether is at least one selected from the group consisting of compounds with the structure represented by Formula III:
R.sup.1—O—CH.sub.2—CH.sub.2—O—R.sup.2  Formula III; wherein, R.sup.1 is selected from the group consisting of alkyl groups with carbon atoms from 1 to 20, and R.sup.2 is selected from the group consisting of alkyl groups with carbon atoms from 1 to 20.

3. The method according to claim 2, wherein R.sup.1 is any one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, and n-butyl; and R.sup.2 is any one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, and n-butyl.

4. The method according to claim 1, wherein the acidic molecular sieve is one or more selected from the group consisting of molecular sieves with structural types of MWW, FER, MFI, MOR, FAU, and BEA.

5. The method according to claim 1, wherein the acidic molecular sieve includes one or more selected from the group consisting of hydrogen-type MCM-22 molecular sieve, hydrogen-type ferrierite, hydrogen-type ZSM-5 molecular sieve, hydrogen-type mordenite, hydrogen-type Y zeolite, and hydrogen-type Beta molecular sieve.

6. The method according to any one of claims 1, 4 and 5, wherein the atomic ratio of silicon to aluminum in the acidic molecular sieve is that Si:Al is in a range from 4:1 to 140:1.

7. The method according to claim 1, wherein the reaction temperature is in a range from 100° C. to 200° C., and the reaction pressure is in a range from 3.5 Mpa to 8 Mpa; the weight hourly space velocity of the ethylene glycol monoether in the raw material is in a range from 0.5 h.sup.−1 to 5.0 h.sup.−1; and the molar ratio of the monohydric alcohol ether to the ethylene glycol monoether in the raw material is that monohydric alcohol ether:ethylene glycol monoether is in a range from 1:1 to 5:1.

8. The method according to claim 1, wherein the raw material contains a carrier gas; wherein gaseous hourly space velocity of the carrier gas is in a range from 0 h.sup.−1 to 10,000 h.sup.−1; and the carrier gas is one or more selected from the group consisting of nitrogen gas, helium gas and argon gas.

9. The method according to claim 8, wherein the gaseous hourly space velocity of the carrier gas is in a range from 100 h.sup.−1 to 2000 h.sup.−1.

10. The method according to claim 1, wherein the reactor contains one or more fixed bed reactors.

Description

DETAILED DESCRIPTION OF THE EMBODIMENT

[0024] Unless otherwise specified, the raw materials and catalyst in the Examples are commercially available.

[0025] The analytical methods and the calculation method for conversion and selectivity in the Examples are as follows:

[0026] The composition of the gas/liquid phase components was analyzed automatically by using an Agilent7890 gas chromatograph configured with a gas autosampler, an FID detector and a FFAP capillary column.

[0027] In the Examples according to the present application, the conversion of ethylene glycol monoether and the selectivity for the product double end-capped ethylene glycol ether and by-products are calculated on the basis of mass:

Conversion of ethylene glycol monoether=[(mass of ethylene glycol monoether in feedstock)−(mass of ethylene glycol monoether in discharge)]/(mass of ethylene glycol monoether in feedstock)×(100%);

Selectivity for double end-capped ethylene glycol ether=(mass of double end-capped ethylene glycol ether in discharge)/[(mass of all ethylene glycol derivatives in discharge)−(mass of unreacted ethylene glycol monoether in discharge)]×(100%); and

Selectivity for by-products=(mass of by-products in discharge)/[(mass of all ethylene glycol derivatives in discharge)−(mass of unreacted ethylene glycol monoether in discharge)]×(100%).

[0028] As used herein, the ethylene glycol derivatives refer to compounds containing an —O—CH.sub.2—CH.sub.2—O— structure in molecular formula thereof, mainly including double end-capped ethylene glycol ether, 1,4-dioxane, unreacted ethylene glycol monoether, double end-capped diethylene glycol ether, diethylene glycol monoether and ethylene glycol.

[0029] Hereinafter, the present application will be further described with reference to specific Examples. It will be appreciated that these Examples are merely illustrative of the present application and are not intended to limit the scope of the present application.

Example 1

[0030] 50 g of a hydrogen-type MCM-22 molecular sieve catalyst with a silicon/alumina ratio (Si:Al) of 45:1 was calcined under an air atmosphere in a muffle furnace at 550° C. for 5 hours. A portion of the powder sample then was compressed and pulverized to 20 to 40 mesh for activity test. 10 g of the hydrogen-type MCM-22 molecular sieve catalyst sample was weighed, placed into a stainless steel reaction tube with an internal diameter of 8.5 mm, and activated at atmospheric pressure and 550° C. with nitrogen for 4 hours. Then, the temperature (abbreviated as T) was reduced to a reaction temperature of 50° C., the molar ratio (CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH) of the raw materials added was 1:1, and the reaction pressure (abbreviated as P) was 0.1 Mpa. The weight hourly space velocity (abbreviated as WHSV) of ethylene glycol monoether in the raw materials was 0.01 h.sup.−1, and a carrier gas was not used. After the reaction was stable, the product was analyzed by gas chromatography to calculate the conversion of ethylene glycol monoether and selectivity for products. The reaction conditions and results are shown in Table 1.

Example 2

[0031] The reaction of this example was performed in the same manner as described in Example 1, except that the reaction temperature T was 90° C., the reaction pressure P was 0.9 Mpa, the molar ratio (CH.sub.3CH.sub.2OCH.sub.3CH.sub.2:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH) of the raw materials added was 2:1, the WHSV was 0.5 h.sup.−1, the carrier gas was nitrogen, and the gaseous hourly space velocity (abbreviated as GHSV) was 100 h.sup.−1. The reaction conditions and results are shown in Table 1.

Example 3

[0032] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type ferrierite molecular sieve, the Si:Al ratio was 15:1, the reaction temperature T was 300° C., the reaction pressure P was 15 Mpa, the molar ratio (CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH) of the raw materials added was 100:1, the WHSV was 15 h.sup.−1, the carrier gas was nitrogen, and the GHSV was 10,000 h.sup.−1. The reaction conditions and results were shown in Table 1.

Example 4

[0033] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type ferrierite molecular sieve, the Si:Al ratio was 15:1, the reaction temperature T was 250° C., the reaction pressure P was 10 Mpa, the molar ratio (CH.sub.3CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.3:CH.sub.3CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH) of the raw materials added was 50:1, the WHSV was 10 h.sup.−1, the carrier gas was argon, and the GHSV was 5,000 h.sup.−1. The reaction conditions and results were shown in Table 1.

Example 5

[0034] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type ZSM-5 molecular sieve, the Si:Al ratio was 140:1, the reaction temperature T was 100° C., the reaction pressure P was 3.5 Mpa, the molar ratio (CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH) of the raw materials added was 1:1, and the WHSV was 0.5 h.sup.−1. The reaction conditions and results were shown in Table 1.

Example 6

[0035] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type ZSM-5 molecular sieve, the Si:Al ratio was 140:1, the reaction temperature T was 150° C., the reaction pressure P was 5 Mpa, the molar ratio ((CH.sub.3).sub.2CHOCH(CH.sub.3).sub.2:(CH.sub.3).sub.2CHOCH.sub.2CH.sub.2OH) of the raw materials added was 3:1, the WHSV was 2.5 h.sup.−1, the carrier gas was nitrogen, and the GHSV was 1,000 h.sup.−1. The reaction conditions and results were shown in Table 1.

Example 7

[0036] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type mordenite molecular sieve, the Si:Al ratio was 4:1, the reaction temperature T was 200° C., the reaction pressure P was 8 Mpa, the molar ratio (CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH) of the raw materials added was 5:1, the WHSV was 5 h.sup.−1, the carrier gas was helium, and the GHSV was 2,000 h.sup.−1. The reaction conditions and results were shown in Table 1.

Example 8

[0037] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type mordenite molecular sieve, the Si:Al ratio was 4:1, the reaction temperature T was 180° C., the reaction pressure P was 7 Mpa, the molar ratio (CH.sub.3(CH.sub.2).sub.3O(CH.sub.2).sub.3CH.sub.3:CH.sub.3(CH.sub.2).sub.3OCH.sub.2CH.sub.2OH) of the raw materials added was 4:1, the WHSV was 4 h.sup.−1, the carrier gas was helium, and the GHSV was 1,500 h.sup.−1. The reaction conditions and results were shown in Table 1.

Example 9

[0038] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type Y molecular sieve, the Si:Al ratio was 25:1, the reaction temperature T was 130° C., the reaction pressure P was 5 Mpa, the molar ratio (CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH) of the raw materials added was 2:1, the WHSV was 2 h.sup.−1, and a carrier gas was not used. The reaction conditions and results were shown in Table 1.

Example 10

[0039] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type Y molecular sieve, the Si:Al ratio was 25:1, the reaction temperature T was 140° C., the reaction pressure P was 6 Mpa, the molar ratio (CH.sub.3CH.sub.2OCH.sub.2CH.sub.3:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH) of the raw materials added was 2.5:1, the WHSV was 2.5 h.sup.−1, the carrier gas was nitrogen, and the GHSV was 500 h.sup.−1. The reaction conditions and results were shown in Table 1.

Example 11

[0040] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type Beta molecular sieve, the Si:Al ratio was 20:1, the reaction temperature T was 230° C., the reaction pressure P was 2 Mpa, the molar ratio (CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH) of the raw materials added was 15:1, the WHSV was 9 h.sup.−1, the carrier gas was nitrogen, and the GHSV was 3,000 h.sup.−1. The reaction conditions and results were shown in Table 1.

Example 12

[0041] The reaction of this example was performed in the same manner as described in Example 1, except that the catalyst was hydrogen-type Beta molecular sieve, the Si:Al ratio was 20:1, the reaction temperature T was 220° C., the reaction pressure P was 3 Mpa, the molar ratio (CH.sub.3CH.sub.2OCH.sub.2CH.sub.3:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH) of the raw materials added was 25:1, the WHSV was 6 h.sup.−1, the carrier gas was nitrogen, and the GHSV was 1,000 h.sup.−1. The reaction conditions and results were shown in Table 1.

TABLE-US-00001 TABLE 1 Reaction conditions and results of the catalytic reactions in Examples 1-12 Selectivity Con- for double version end- Single- of capped Selectivity pass T ethylene ethylene Selectivity for other lifespan P glycol glycol for 1,4- by- of Ex- WHSV monoether ether dioxane products catalyst ample Catalyst Composition and molar ratio of raw materials GHSV (%) (%) (%) (%) (day) 1 MCM- CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 1:1 50° C. 96.7 92.0 0.3 8.7 160 22 0.1 MPa 0.01 h.sup.−1 0 h.sup.−1 2 MCM- CH.sub.3CH.sub.2OCH.sub.3CH.sub.2:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH = 2:1 90° C. 94.6 92.0 0.3 7.7 150 22 0.9 MPa 0.5 h.sup.−1 100 h.sup.−1 3 Ferrierite CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 100:1 300° C. 97.1 98.0 0.1 1.9 170 15 MPa 15 h.sup.−1 10,000 h.sup.−1 4 Ferrierite CH.sub.3CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.3:CH.sub.3CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH = 250° C. 98.1 98.8 0.1 1.1 200 50:1 10 MPa 10 h.sup.−1 5,000 h.sup.−1 5 ZSM-5 CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 1:1 100° C. 96.2 97.6 0.2 2.2 210 3.5 MPa 0.5 h.sup.−1 0 h.sup.−1 6 ZSM-5 (CH.sub.3).sub.2CHOCHCH.sub.3).sub.2:(CH.sub.3).sub.2CHOCH.sub.2CH.sub.2OH = 3:1 150° C. 98.3 97.2 0.3 2.5 150 5 MPa 2.5 h.sup.−1 1,000 h.sup.−1 7 Mordenite CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 5:1 200° C. 98.8 99.0 0.1 0.9 200 8 MPa 5 h.sup.−1 2,000 h.sup.−1 8 Mordenite CH.sub.3(CH.sub.2).sub.3O(CH.sub.2).sub.3CH.sub.3:CH.sub.3(CH.sub.2).sub.3OCH.sub.2CH.sub.2OH = 4:1 180° C. 95.5 97.1 0.3 2.6 190 7 MPa 4 h.sup.−1 1,500 h.sup.−1 9 Y CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 2:1 130° C. 94.3 96.9 0.2 2.9 300 molecular 5 MPa sieve 2 h.sup.−1 0 h.sup.−1 10 Y CH.sub.3CH.sub.2OCH.sub.2CH.sub.3:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH = 2.5:1 140° C. 92.0 95.3 0.4 4.3 220 molecular 6 MPa sieve 2.5 h.sup.−1 500 h.sup.−1 11 Beta CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 15:1 230° C. 92.7 96.1 0.4 3.5 160 2 MPa 9 h.sup.−1 3,000 h.sup.−1 12 Beta CH.sub.3CH.sub.2OCH.sub.2CH.sub.3:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH = 25:1 220° C. 93.1 97.1 0.3 2.6 150 3 MPa 6 h.sup.−1 1,000 h.sup.−1 Note: The other by-products were mainly double end-capped diethylene glycol ether, diethylene glycol monoether and ethylene glycol.

Comparative Example 1

[0042] 50 g of perfluorinated sulfonic acid resin (Nafion-H) bought from DuPont Company was dried under an air atmosphere in an air dry oven at 105° C. for 12 hours. After cooling, 10 g of the sample was weighed, placed into a stainless steel reaction tube with an internal diameter of 8.5 mm for activity test, and activated at atmospheric pressure and 100° C. with nitrogen for 1 hour. Then, the catalytic reaction was performed, and the reaction temperature (T) was 130° C., the molar ratio (CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH) of the raw materials added was 2:1, the reaction pressure (P) was 5 Mpa, the weight hourly space velocity (WHSV) of methylal was 2 h.sup.−1, and a carrier gas was not used. After the reaction was stable, the product was analyzed by gas chromatography to calculate the conversion of ethylene glycol monoether and selectivity for products. The reaction conditions and results were shown in Table 2.

Comparative Example 2

[0043] The reaction of this example was performed in the same manner as described in Comparative example 1, except that the reaction temperature T was 140° C., the reaction pressure P was 6 Mpa, the molar ratio (CH.sub.3CH.sub.2OCH.sub.2CH.sub.3:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH) of the raw materials added was 2.5:1, the WHSV was 2.5 h.sup.−1, the carrier gas was nitrogen, and the GHSV was 500 h.sup.−1. The reaction conditions and results were shown in Table 2.

Comparative Example 3

[0044] The reaction of this example was performed in the same manner as described in Comparative example 1, except that the catalyst was sulfonated styrene-divinylbenzene copolymer (Amberlyst-15) resin bought from Rohm and Haas Company. The reaction conditions and results were shown in Table 2.

Comparative Example 4

[0045] The reaction of this example was performed in the same manner as described in Comparative example 2, except that the catalyst was sulfonated styrene-divinylbenzene copolymer (Amberlyst-15) resin bought from Rohm and Haas Company. The reaction conditions and results were shown in Table 2.

Comparative Example 5

[0046] The reaction of this example was performed in the same manner as described in Comparative example 1, except that the catalyst was sulfonated styrene-divinylbenzene copolymer strongly acidic cation exchange resin (D005) bought from Dandong Pearl Specialty Resin Co., Ltd. The reaction conditions and results were shown in Table 2.

Comparative Example 6

[0047] The reaction of this example was performed in the same manner as described in Comparative example 2, except that the catalyst was sulfonated styrene-divinylbenzene copolymer strongly acidic cation exchange resin (D005) bought from Dandong Pearl Specialty Resin Co., Ltd. The reaction conditions and results were shown in Table 2.

TABLE-US-00002 TABLE 2 The reaction conditions and results of the catalytic reactions in Comparative Examples 1-6 Selectivity for double Conversion end- Single- of capped pass T ethylene ethylene Selectivity Selectivity lifespan Com- P glycol glycol for 1,4- for other of parative WHSV monoether ether dioxane by-products catalyst Example Catalyst Composition and molar ratio of raw materials GHSV (%) (%) (%) (%) (day) 1 Nafion CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 2:1 130° C. 43.6 63.2 27.8 9.0 3 5 MPa 2 h.sup.−1 0 h.sup.−1 2 Nafion CH.sub.3CH.sub.2OCH.sub.2CH.sub.3:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH = 140° C. 37.1 77.7 17.5 4.8 4 2.5:1 6 MPa 2.5 h.sup.−1 500 h.sup.−1 3 Amberlyst- CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 2:1 130° C. 38.8 70.5 20.8 8.7 3 15 5 MPa 2 h.sup.−1 0 h.sup.−1 4 Amberlyst- CH.sub.3CH.sub.2OCH.sub.2CH.sub.3:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH = 140° C. 40.0 72.1 18.5 9.4 3 15 2.5:1 6 MPa 2.5 h.sup.−1 500 h.sup.−1 5 D005 CH.sub.3OCH.sub.3:CH.sub.3OCH.sub.2CH.sub.2OH = 2:1 130° C. 50.1 77.9 17.6 4.5 5 5 MPa 2 h.sup.−1 0 h.sup.−1 6 D005 CH.sub.3CH.sub.2OCH.sub.2CH.sub.3:CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OH = 140° C. 48.5 79.1 15.8 5.1 6 2.5:1 6 MPa 2.5 h.sup.−1 500 h.sup.−1 Note: The other by-products were mainly double end-capped diethylene glycol ether, diethylene glycol monoether and ethylene glycol.

Example 13

[0048] The catalysts inactivated in the single-pass reactions in Examples 1, 3, 5, 7, 9 and 11 were removed and regenerated, with the regeneration conditions that the catalysts were calcined at 550° C. for 4 hours under an air atmosphere. The regenerated catalysts were used again according to the reaction conditions of the example from which the catalyst was obtained. The results were shown in Table 3.

TABLE-US-00003 TABLE 3 Comparison of the reaction results of the catalysts in the examples before and after regeneration Conversion of ethylene Selectivity for double end-capped glycol monoether (%) ethylene glycol ether (%) Reaction First After First After Catalysts conditions reaction regeneration reaction regeneration MCM-22 Same as those in 96.7 97.2 92.0 93.0 Example 1  Ferrierite Same as those in 97.1 97.3 98.0 98.5 Example 3  ZSM-5 Same as those in 96.2 97.8 97.6 98.0 Example 5  Mordenite Same as those in 98.8 98.7 99.0 99.0 Example 7  Y molecular Same as those in 94.3 95.0 96.9 97.5 sieve Example 9  Beta Same as those in 92.7 94.1 96.1 96.5 Example 11

[0049] The resin catalysts of the Comparative Examples cannot be regenerated.

[0050] It will be understood that the foregoing Examples are only some examples of the present application, rather than limit the present application in any form. Although the optimized examples of the present application are illustrated as above, they are not intended to limit the present application. In view of the instant disclosure, modifications or changes may be made by those skilled in the art without departing from the spirit and purview of the present application, and those modifications or changes are equivalent embodiments of the present application, falling into the scope of the appended claims.