CN111196752A - Process for preparing alkyldiglycol - Google Patents
Process for preparing alkyldiglycol Download PDFInfo
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- CN111196752A CN111196752A CN201911125755.3A CN201911125755A CN111196752A CN 111196752 A CN111196752 A CN 111196752A CN 201911125755 A CN201911125755 A CN 201911125755A CN 111196752 A CN111196752 A CN 111196752A
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- Prior art keywords
- alkyldiglycol
- catalyst
- aluminum
- alcohol
- producing
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- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical group [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- -1 alkyl diglycol Chemical compound 0.000 description 6
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- MXVMODFDROLTFD-UHFFFAOYSA-N 2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound CCCCOCCOCCOCCOCCO MXVMODFDROLTFD-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for preparing alkyldiglycol in the presence of a novel aluminum-based catalyst containing an alkali metal or alkaline earth metal, which has an NRE (Narrow distribution Ethoxylate Narrow Range Ethoxylate, Narrow molar distribution) effect while increasing the reaction rate.
Description
Technical Field
The present invention relates to a method for preparing alkyldiglycol (ALKYL DIGLYCOL) in the presence of a novel aluminum-based catalyst. More particularly, the present invention relates to a method for preparing alkyldiglycol in the presence of a novel aluminum-based catalyst, which has NRE (Narrow distribution ethoxylate Narrow range ethoxylate, Narrow molar distribution) effect and simultaneously increases reaction speed.
Background
The invention relates to a method for preparing alkyl diglycol from alcohol and alkylene oxide.
For example, the reaction for producing diethylene glycol butyl ether from butanol and Ethylene Oxide (EO) is as follows.
As an aluminum catalyst widely used in the above reaction, a Mg — Al catalyst showing selectivity (NRE effect) for addition of 2 moles of alkylene oxide (alkylene oxide) is known. However, since this catalyst is a heterogeneous catalyst in the form of a composite oxide, it is not suitable for a continuous production process. Further, the aluminum alkoxide catalyst as a homogeneous catalyst exhibits NRE effect, but has a problem of remarkably slow reaction speed.
Therefore, in the production of alkyldiglycols from alcohols and alkylene oxides, it is necessary to develop a catalyst capable of increasing the productivity of alkyldiglycols.
Patent document 1: JP3174479B2
Disclosure of Invention
The purpose of the present invention is to provide a novel aluminum-based catalyst which, when alkyl diglycol is produced from an alcohol and an alkylene oxide, improves the reaction rate while maintaining the selectivity of the aluminum-based catalyst for addition of 2 moles of alkylene oxide (NRE effect).
In order to solve the above problems, the present invention provides a method for preparing alkyldiglycol, comprising the following reaction: an alcohol is reacted with an alkylene oxide in the presence of a catalyst selected from an aluminum compound containing an alkali metal and an alkaline earth metal or a hydrate thereof.
According to one embodiment, the aluminum-based catalyst can be potassium aluminum sulfate (KAl (SO)4)2) Or a hydrate thereof.
According to an embodiment, the alcohol may be selected from alkyl alcohols having 1 to 6 carbon atoms.
According to an embodiment, the alkylene oxide may be selected from alkylene oxides having 2 to 4 carbon atoms.
According to an embodiment, the reaction may be performed at a temperature of 170 ℃ to 210 ℃.
According to one embodiment, it may be at 3kg/cm2G to 30kg/cm2G under pressure.
According to an embodiment, the alkylene oxide may be used in a molar ratio of 3:1 to 8:1 with respect to the alcohol.
According to an embodiment, 20ppm to 400ppm of the catalyst may be used with respect to the weight of the alcohol.
The novel aluminum catalyst of the present invention exerts the following effects: in the production of alkyldiglycol, the reaction rate is improved while maintaining the selectivity of the aluminum catalyst for addition of 2 mol of alkylene oxide (NRE effect).
Drawings
FIG. 1 is a graph showing EO conversion ratios of catalysts used in examples and comparative examples.
Detailed Description
The invention relates to a preparation method of alkyl diglycol, which comprises the following reaction: reacting an alcohol with an alkylene oxide in the presence of an aluminum catalyst selected from aluminum compounds and hydrates thereof.
According to an embodiment, the present invention provides a method for preparing butyl diglycol, comprising the following reaction: butanol is reacted with ethylene oxide in the presence of a catalyst selected from potassium aluminum sulfate or hydrates thereof.
The aluminum-based catalyst is an aluminum-based catalyst containing an alkali metal (group 1 metal of the chemical periodic table) or an alkaline earth metal (group 2 metal of the chemical periodic table). According to one embodiment, the aluminum-based catalyst is potassium aluminum sulfate or a hydrate thereof.
The alcohol may be selected from alkyl alcohols having 1 to 6 carbon atoms. According to one embodiment, the alcohol is 1-butanol.
The alkylene oxide may be selected from alkylene oxides having 2 to 4 carbon atoms. According to an embodiment, the alkylene oxide is ethylene oxide.
The alkylene oxide may be used in a molar ratio of 3:1 to 8:1 relative to the alcohol. According to an embodiment, the molar ratio of the alkylene oxide to the alcohol is from 5:1 to 7: 1.
When the molar ratio is out of the range, there is a problem that the product productivity is lowered due to, for example, a large content of a high molecular weight.
The aluminum-containing catalyst may be used in an amount of 20ppm or more based on the weight of the alcohol. According to one embodiment, more than 200ppm of the catalyst may be used relative to the weight of alcohol. According to one embodiment, less than 400ppm of said catalyst may be used with respect to the alcohol weight. When the concentration of the catalyst is out of the above range, there is a possibility that the high molecular weight content is increased or the reaction rate is decreased.
In the present invention, in the presence of an aluminum-based catalyst and at a temperature of 170 ℃ to 210 ℃ and 3kg/cm2G to 30kg/cm2G reacting the alcohol and the alkylene oxide. According to an embodiment, the temperature is 170 ℃ to 190 ℃. According to an embodiment, the pressure is 3kg/cm2G to 10kg/cm2G。
In the present invention, an aluminum catalyst is used as the catalyst, and thus the conversion rate of alkylene oxide can be improved.
The operation and effect of the present invention will be described in more detail with reference to the following specific examples. However, this embodiment is provided as an example of the present invention, and the scope of the claims of the present invention is not limited to this embodiment in some sense.
Examples
Example (Potassium aluminum sulfate catalyst used alone)
500g of butanol, 0.1g of potassium aluminum sulfate and 50g of ethylene oxide were charged into an autoclave reactor and heated at 5kg/cm2G was stirred under pressure at 170 ℃ for 24 hours to react. The obtained product was analyzed by GC (50 ℃ → 10 ℃/min → 300 ℃, Hold), and the amounts of the respective components in the product produced with the reaction time are shown in table 1 below.
[ Table 1]
[ weight% ]
| 3 |
6 |
9 |
12 |
24 hours | |
| BG | 93.1 | 92.3 | 92.2 | 91.9 | 91.7 |
| BDG | 6.63 | 7.30 | 7.37 | 7.74 | 7.82 |
| BTG | 0.32 | 0.37 | 0.40 | 0.37 | 0.41 |
| B4G | 0 | 0.04 | 0 | 0.02 | 0.02 |
BG: ethylene glycol butyl ether
BDG: diethylene glycol butyl ether
BTG: triethylene glycol butyl ether
B4G: tetraethylene glycol butyl ether
Comparative example 1 (Tributoxyaluminum catalyst used alone)
The same reaction as in example 1 was carried out, except that 0.1g of tributoxyaluminum was used instead of 0.1g of potassium aluminum sulfate in example 1 described above. The obtained product was analyzed, and the amounts of the respective components in the product produced with the lapse of reaction time are shown in table 2 below.
[ Table 2]
[ weight% ]
| 3 |
6 |
9 |
12 |
24 hours | |
| BG | 97.33 | 95.85 | 95.07 | 94.59 | 94.07 |
| BDG | 2.6 | 3.98 | 4.73 | 5.17 | 5.64 |
| BTG | 0.07 | 0.13 | 0.17 | 0.20 | 0.23 |
| B4G | 0 | 0.05 | 0.04 | 0.05 | 0.06 |
Comparative example 2 (Tributoxyaluminum catalyst and acetic acid cocatalyst were used in combination)
The same reaction as in example 1 was carried out, except that 0.1g of tributoxyaluminum and 0.1g of acetic acid were used instead of 0.1g of potassium aluminum sulfate in the above example 1. The obtained product was analyzed, and the amounts of the respective components in the product produced with the lapse of reaction time are shown in table 3 below.
[ Table 3]
[ weight% ]
| 3 |
6 |
9 |
12 |
24 hours | |
| BG | 97.75 | 96.87 | 96.16 | 95.79 | 95.02 |
| BDG | 2.2 | 3.06 | 3.72 | 4.02 | 4.74 |
| BTG | 0.05 | 0.07 | 0.10 | 0.19 | 0.20 |
| |
0 | 0 | 0.02 | 0.02 | 0.04 |
The reaction completion time is a time at which the pressure does not change during the reaction, and this time is a time at which the EO conversion rate is 100%.
When only tributoxyaluminum was used as the catalyst, it took about 18 hours until the end of the reaction, but when the potassium aluminum sulfate catalyst according to the present invention was used, the reaction was completed in about 10 hours, which indicates that the effect of improving the reaction rate of the potassium aluminum sulfate catalyst was excellent. In the case where acetic acid was added as a co-catalyst, there was no reaction rate-improving effect, but rather a lower rate than that in the case where aluminum tributoxide was used alone was exhibited. Shows the result that the selectivity to 1 mole of alkylene oxide is higher than the selectivity to 2 moles of alkylene oxide which is the object of the present invention.
From the above results, it is understood that the reaction rate is improved when the potassium aluminum sulfate catalyst of the present invention is used, as compared with the catalyst in the form of aluminum alkoxide which is known as a conventional aluminum-based catalyst.
Claims (8)
1. A process for the preparation of an alkyldiglycol comprising the reaction of:
an alcohol is reacted with an alkylene oxide in the presence of an aluminum-based catalyst selected from an aluminum-based compound containing an alkali metal or an alkaline earth metal or a hydrate thereof.
2. The process for producing alkyldiglycol according to claim 1, wherein,
the aluminum catalyst is potassium aluminum sulfate KAl (SO)4)2Or a hydrate thereof.
3. The process for producing alkyldiglycol according to claim 1, wherein,
the alcohol is selected from alkyl alcohols having 1 to 6 carbon atoms.
4. The process for producing alkyldiglycol according to claim 1, wherein,
the alkylene oxide is selected from alkylene oxides having 2 to 4 carbon atoms.
5. The process for producing alkyldiglycol according to claim 1, wherein,
the reaction is carried out at a temperature of 170 ℃ to 210 ℃.
6. The process for producing alkyldiglycol according to claim 1, wherein,
at 3kg/cm2G to 30kg/cm2G under pressure.
7. The process for producing alkyldiglycol according to claim 1, wherein,
the alkylene oxide is used in a molar ratio of 3:1 to 8:1 relative to the alcohol.
8. The process for producing alkyldiglycol according to claim 1, wherein,
from 20ppm to 400ppm of the catalyst relative to the weight of alcohol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2018-0141207 | 2018-11-16 | ||
| KR1020180141207A KR20200057185A (en) | 2018-11-16 | 2018-11-16 | Method for producing alkyl diglycol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111196752A true CN111196752A (en) | 2020-05-26 |
Family
ID=70744324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911125755.3A Pending CN111196752A (en) | 2018-11-16 | 2019-11-18 | Process for preparing alkyldiglycol |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20200057185A (en) |
| CN (1) | CN111196752A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3174479B2 (en) | 1995-03-28 | 2001-06-11 | ライオン株式会社 | Method for producing alkylene oxide adduct of compound having active hydrogen |
-
2018
- 2018-11-16 KR KR1020180141207A patent/KR20200057185A/en unknown
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2019
- 2019-11-18 CN CN201911125755.3A patent/CN111196752A/en active Pending
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| Publication number | Publication date |
|---|---|
| KR20200057185A (en) | 2020-05-26 |
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| PB01 | Publication | ||
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Application publication date: 20200526 |