CN101921180B - Method for synthesizing butyl cellosolve - Google Patents
Method for synthesizing butyl cellosolve Download PDFInfo
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- CN101921180B CN101921180B CN 201010252085 CN201010252085A CN101921180B CN 101921180 B CN101921180 B CN 101921180B CN 201010252085 CN201010252085 CN 201010252085 CN 201010252085 A CN201010252085 A CN 201010252085A CN 101921180 B CN101921180 B CN 101921180B
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Abstract
The invention relates to a method for synthesizing butyl cellosolve, which is characterized by comprising the following steps of: adding butanol and a catalyst into a reaction kettle, sealing, agitating, heating to set reaction temperature and stopping heating; controlling reaction pressure at 0.1-0.5 MPa, and continuously introducing ethylene oxide into the reaction kettle according to the molar ratio of butanol to ethylene oxide equaling to (5-1):1; after completing the introduction of the ethylene oxide, maintaining temperature until the temperature in the kettle does not rise any more and the pressure in the kettle does not descend any more, and introducing cooling water to cool the discharged material to obtain butyl cellosolve. The catalyst is a supported potassium fluoride/aluminum oxide solid base catalyst. The method has the advantages of simple process, low equipment investment, low energy consumption, low material consumption, high EO (Ethylene Oxide) conversion rate and good environmental protection; moreover, the catalyst can be repeatedly used, so that the production cost is effectively reduced.
Description
(1) technical field
The present invention relates to a kind of method of synthesizing butyl cellosolve.Belong to technology of fine chemicals.
(2) background technology
(Ethylene glycol monobutyl ether, EGBE), the another name ethylene glycol butyl ether is a kind of colourless inflammable liquid to butyl glycol ether, is dissolved in most of organic solvents and mineral oil.EGBE is one of essential industry derivative of epoxy compounds, is very important fine chemicals.Because the group---ehter bond and the hydroxyl that have two strong dissolving functions on its chemical structure, the former has lipophilicity, solubilized hydrophobic nature compound, latter's possess hydrophilic property, the solubilized hydrophilic compounds, thereby have very strong dissolving power, have the title of " menstruum universale ".
Abroad since the mid-1970s brought into use EGBE to make solvent, EGBE had obtained using widely in industries such as paint, leather, coating, weaving, organic chemical industries.Domestic market EGBE product import volume still increases year by year at present, therefore, develops this product and the corresponding catalytic reaction process of research, has and wide application prospect.
The synthetic of EGBE is typical etherification reaction, and the at present industrial potassium hydroxide that adopt are made catalyzer more.Although potassium hydroxide has catalytic activity height, short advantage of reaction times, but also exist the not easily separated and recovery of catalyzer, the wide problem of products distribution, and there are problems such as equipment corrosion, environmental pollution, need badly and adopt pollution-free, the segregative new catalyst of no burn into to replace it, the employing solid base catalyst be get rid of of traditional etherification reaction technology drawback effective by way of.
(3) summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, a kind of method of synthesizing butyl cellosolve is provided, this method technology is simple, and facility investment is few, and energy consumption, material consumption are low, EO transformation efficiency height, and the feature of environmental protection is good, and can repeat repeatedly to use, and has reduced production cost effectively.
The object of the present invention is achieved like this: a kind of method of synthesizing butyl cellosolve, butanols and catalyzer are added in the reactor, stir airtight back, stops heating after heating to the temperature of reaction of setting simultaneously, and the control reaction pressure is 0.1～0.5MPa, it is 5～1: 1 ratio in butanols and EO mol ratio, continue in reactor, to feed EO, after EO imports and finishes, be incubated to temperature in the kettle no longer rise, when the still internal pressure no longer descends, logical water quench to 60 ℃ discharging obtains EGBE.
Described catalyzer is loading type Potassium monofluoride/aluminum oxide solid base catalyst.
Described Preparation of catalysts condition: 300～700 ℃ of maturing temperatures, Potassium monofluoride charge capacity 20～50%, alumina catalyst support (Al
2O
3) 50～80%.
Catalyzer provided by the present invention prepares in accordance with the following methods: carrier A l
2O
3Place retort furnace in 550 ℃ of activation 4h, with KFH
2O is dissolved in the 200mL ethanol, adds phase-transfer catalyst polyoxyethylene glycol-400 and (accounts for KFH
2O and Al
2O
3Total mass 5%), add the Al after the activation again
2O
3Carrier, 60 ℃ are stirred dipping 3h down, are heated to 100 ℃ and boil off the second alcohol and water, and wet sample places retort furnace with certain maturing temperature roasting 6h in 120 ℃ of following vacuum-drying 12h, obtains loading type Potassium monofluoride/aluminum oxide solid base catalyst.
As a step more of the present invention is limited, temperature of reaction is 90～130 ℃ in the method for the present invention, and catalyst levels is 0.2～1.0% of reactant total mass.
When adopting pickling process that KF is loaded on aluminum oxide surperficial, the adding of organic polar solvent ethanol and phase-transfer catalyst polyoxyethylene glycol-400, making residually on the carrier surface has-OH, the F-that these hydroxyls can discharge with the KF on alumina catalyst support surface forms [Al-OH ... F-] the class material, KF dispersity and catalyst surface area are increased, in addition, KF and aluminum-oxygen tetrahedron interact after high-temperature roasting and have generated K
3AlF
6, because KF and K
3AlF
6Synergy, thereby formed the active site of a series of dispersions at catalyst surface, constituted the active centre of solid base catalyst, during catalyzed reaction and the butanols effect form the alkoxyl group negatively charged ion, remove attack oxyethane again, carry out nucleophilic substitution by the SN2 course, the product negatively charged ion of formation obtains H+ and generates butyl glycol ether at catalyst surface again.
Compared with prior art, the invention has the beneficial effects as follows:
1, because catalyzer adopts solid base catalyst, do not dissolve in the reaction process, it is namely separable that after-filtration is finished in reaction, is easy to remove, and reduces energy consumption.
2, do not need N-process in the reaction, synthetic EGBE product does not have soda acid and discharge of wastewater, non-environmental-pollution.
3, EO transformation efficiency height can be up to 99.47%, and no side reaction takes place.
4, catalyst activity height, usage quantity is few, and can reuse, and the catalyzer cost is low.
(4) embodiment
The invention will be further described by following example, but not thereby limiting the invention.
Among the embodiment, butanols and EO are analytical pure, and EO produces for raising sub-petro-chemical corporation.
Among the embodiment, reactor is the GSH-2 type stainless steel cauldron that Weihai Chemical Machinery Co., Ltd. produces, its volume 2L.Reactor is furnished with spiral coil cooling tube, by the water yield in the control feeding spiral coil cooling tube, can in time take away the heat in the reactor, thereby reach the purpose of control temperature of reaction.
Among the embodiment, the concentration of each material of reaction back is carried out quantitative analysis with gas chromatograph.Adopt GC9790 type gas chromatograph, split stream sampling is furnished with the temperature programming parts, flame ionization ditector.Capillary chromatograph is ATSE-54 type 25m * 0.20mm * 0.33 μ m.
Among the embodiment, the transformation efficiency of EO calculates by following formula:
EO transformation efficiency=(the total charging capacity of EO amount/EO of having reacted) * 100%
EGBE selectivity=(the EO total amount of the EO amount/participation reaction of EGBE combination) * 100%
Among the embodiment, catalyzer prepares in accordance with the following methods, takes by weighing 70.0g carrier A l
2O
3550 ℃ of activation 4h in retort furnace.With 48.6gKFH
2O is dissolved in the 200mL ethanol, adds 5g polyoxyethylene glycol-400, adds the Al after activating
2O
3Carrier, 60 ℃ are stirred down dipping 3h, are heated to 100 ℃ and boil off the second alcohol and water, and wet sample is in 120 ℃ of following vacuum-drying 12h, places retort furnace with 600 ℃ maturing temperature roasting 6h, obtains loading type Potassium monofluoride/aluminum oxide solid base catalyst.
Embodiment 1
1.1611g catalyzer and 207.5g butanols are joined in the reactor that volume is 2L, stir, heat up in airtight back, when temperature reaches 90 ℃, stop heating, continue in reactor, to import EO 24.68g, this moment, the mol ratio of butanols and EO was 5: 1, and the control still is pressed 0.1～0.5MPa, and by regulating the water yield that feeds in the reactor spiral coil cooling tube that temperature of reaction is constant in 90 ℃.After reaction finished, the EO transformation efficiency was that the selectivity of 64.29%, EGBE is 74.11%.
Embodiment 2
1.1611g catalyzer and 207.5g butanols are joined in the reactor that volume is 2L, stir, heat up in airtight back, when temperature reaches 100 ℃, stop heating, continue in reactor, to import EO, the mol ratio of control butanols and EO is 4: 1, and the control still is pressed 0.1～0.5MPa, and by regulating the water yield that feeds in the reactor spiral coil cooling tube that temperature of reaction is constant in 100 ℃.After reaction finished, the EO transformation efficiency was that the selectivity of 87.60%, EGBE is 68.00%.
Embodiment 3
1.1611g catalyzer and 207.5g butanols are joined in the reactor that volume is 2L, stir, heat up in airtight back, when temperature reaches 110 ℃, stop heating, continue in reactor, to import EO24.68g, this moment, the mol ratio of butanols and EO was 5: 1, and the control still is pressed 0.1～0.5MPa, and by regulating the water yield that feeds in the reactor spiral coil cooling tube that temperature of reaction is constant in 110 ℃.After reaction finished, the EO transformation efficiency was that the selectivity of 99.47%, EGBE is 66.65%.
Embodiment 4
1.1611g catalyzer and 207.5g butanols are joined in the reactor that volume is 2L, stir, heat up in airtight back, when temperature reaches 120 ℃, stop heating, continue in reactor, to import EO, the mol ratio of control butanols and EO is 1: 1, and the control still is pressed 0.1～0.5MPa, and by regulating the water yield that feeds in the reactor spiral coil cooling tube that temperature of reaction is constant in 120 ℃.After reaction finished, the transformation efficiency of EO was that the selectivity of 78.85%, EGBE is 70.30%.
Embodiment 5
1.1611g catalyzer and 207.5g butanols are joined in the reactor that volume is 2L, stir, heat up in airtight back, when temperature reaches 130 ℃, stop heating, continue in reactor, to import EO, the mol ratio of control butanols and EO is 2: 1, and the control still is pressed 0.1～0.5MPa, and by regulating the water yield that feeds in the reactor spiral coil cooling tube that temperature of reaction is constant in 130 ℃.After reaction finished, the transformation efficiency of EO was that the selectivity of 78.32%, EGBE is 71.45%.
Embodiment 6
0.4644g catalyzer and 207.5g butanols are joined in the reactor that volume is 2L, stir, heat up in airtight back, when temperature reaches 110 ℃, stop heating, continue in reactor, to import EO24.68g, this moment, the mol ratio of butanols and EO was 5: 1, and the control still is pressed 0.1～0.5MPa, and by regulating the water yield that feeds in the reactor spiral coil cooling tube that temperature of reaction is constant in 110 ℃.After reaction finished, the transformation efficiency of EO was that the selectivity of 85.47%, EGBE is 68.13%.
Embodiment 7
1.6254g catalyzer and 207.5g butanols are joined in the reactor that volume is 2L, stir, heat up in airtight back, when temperature reaches 110 ℃, stop heating, continue in reactor, to import EO24.68g, this moment, the mol ratio of butanols and EO was 5: 1, and the control still is pressed 0.1～0.5MPa, and by regulating the water yield that feeds in the reactor spiral coil cooling tube that temperature of reaction is constant in 110 ℃.After reaction finished, the transformation efficiency of EO was that the selectivity of 85.14%, EGBE is 69.46%.
Embodiment 8
2.322g catalyzer and 207.5g butanols are joined in the reactor that volume is 2L, stir, heat up in airtight back, when temperature reaches 110 ℃, stop heating, continue in reactor, to import EO 24.68g, this moment, the mol ratio of butanols and EO was 5: 1, and the control still is pressed 0.1～0.5MPa, and by regulating the water yield that feeds in the reactor spiral coil cooling tube that temperature of reaction is constant in 110 ℃.After reaction finished, the transformation efficiency of EO was that the selectivity of 79.18%, EGBE is 70.32%.
Claims (5)
1. the method for a synthesizing butyl cellosolve, it is characterized in that: butanols and catalyzer are added in the reactor, stir airtight back, stop heating after heating to the temperature of reaction of setting simultaneously, the control reaction pressure is 0.1～0.5MPa, be 5～1: 1 by butanols and oxyethane mol ratio, continue in reactor, to feed oxyethane, after oxyethane imports and finishes, be incubated to temperature in the kettle no longer rise, when the still internal pressure no longer descends, logical water quench discharging obtains butyl glycol ether, and described catalyzer is loading type Potassium monofluoride/aluminum oxide solid base catalyst; The preparation method of described loading type Potassium monofluoride/aluminum oxide solid base catalyst is: carrier A l
2O
3Place 550 ℃ of calcination activation 4h of retort furnace, with KFH
2O is dissolved in the 200mL ethanol, adds phase-transfer catalyst polyoxyethylene glycol-400, adds the Al after activating
2O
3Carrier, 60 ℃ are stirred dipping 3h down, are heated to 100 ℃ and boil off the second alcohol and water, and wet sample places retort furnace with certain maturing temperature roasting 6h in 120 ℃ of following vacuum-drying 12h, obtains loading type Potassium monofluoride/aluminum oxide solid base catalyst.
2. the method for a kind of synthesizing butyl cellosolve according to claim 1, it is characterized by: the temperature of reaction of described setting is 90～130 ℃, catalyst levels is 0.2～1.0% of reactant total mass.
3. the method for a kind of synthesizing butyl cellosolve according to claim 2, it is characterized by: the temperature of reaction of described setting is 110 ℃, catalyst levels is 0.3% of reactant total mass.
4. the method for a kind of synthesizing butyl cellosolve according to claim 2 is characterized by: ℃ discharging of described water quench to 60.
5. the method for a kind of synthesizing butyl cellosolve according to claim 3 is characterized by: ℃ discharging of described water quench to 60.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762578A (en) * | 2005-09-28 | 2006-04-26 | 茂名学院 | Supported solid alkali catalyst for synthesis of propylene glycol |
| CN101121646A (en) * | 2007-09-14 | 2008-02-13 | 胡先念 | Method for preparing ethylene glycol monobutyl ether |
| CN101337864A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Method for preparing ethylene glycol mono-n-butyl ether by continuous pipe reaction |
-
2010
- 2010-08-12 CN CN 201010252085 patent/CN101921180B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762578A (en) * | 2005-09-28 | 2006-04-26 | 茂名学院 | Supported solid alkali catalyst for synthesis of propylene glycol |
| CN101121646A (en) * | 2007-09-14 | 2008-02-13 | 胡先念 | Method for preparing ethylene glycol monobutyl ether |
| CN101337864A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Method for preparing ethylene glycol mono-n-butyl ether by continuous pipe reaction |
Non-Patent Citations (2)
| Title |
|---|
| 新型固体酸催化丁醇和环氧乙烷醚化;毛连山等;《化学工业与工程技术》;20060630;第27卷(第3期);第26-27页 * |
| 毛连山等.新型固体酸催化丁醇和环氧乙烷醚化.《化学工业与工程技术》.2006,第27卷(第3期),第26-27页. |
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Address after: 214444, Jiangsu Province, Jiangyin City West Li Zhuang Town West ball Zhuang No. 1 Applicant after: Jiangsu Yida Chemical Co., Ltd. Applicant after: Changzhou University Address before: 214444, Jiangsu Province, Jiangyin City West Li Zhuang Town West ball Zhuang No. 1 Applicant before: Yida Chemical Co., Ltd. Applicant before: Changzhou University |
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Effective date of registration: 20160701 Address after: 132105 No. 346, Kunlun street, Jilin economic and Technological Development Zone, Jilin Patentee after: Jilin Yida Chemical Co., Ltd. Address before: 214444, Jiangsu Province, Jiangyin City West Li Zhuang Town West ball Zhuang No. 1 Patentee before: Jiangsu Yida Chemical Co., Ltd. Patentee before: Changzhou University |