CN1775355A - Organic solid base catalyst for synthesizing propylene glycol ether and its preparing method and use - Google Patents
Organic solid base catalyst for synthesizing propylene glycol ether and its preparing method and use Download PDFInfo
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- CN1775355A CN1775355A CN 200510048149 CN200510048149A CN1775355A CN 1775355 A CN1775355 A CN 1775355A CN 200510048149 CN200510048149 CN 200510048149 CN 200510048149 A CN200510048149 A CN 200510048149A CN 1775355 A CN1775355 A CN 1775355A
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Abstract
The present invention relates to a solid alkaline catalyst for synthesizing propylene glycol ether. It uses quaternary ammonium hydroxide as active component, and uses MCM-41 as carrier, the quaternary ammonium hydroxide grafting quantity is 0.5-1.5mmol/g. Said invention uses chloropropyl trimethoxysilane as coupling agent and uses cyclohexane as solvent, and adopts ultrasonic technique to make the quaternary ammonium hydroxide be simply and moderately grafted on the carrier MCM-41 so as to obtain the invented catalyst.
Description
Technical field
The invention belongs to a kind of catalyst and method for making and application, relate in particular to a kind of being used for propylene oxide method synthesis of propylene glycol solid catalyst and preparation method and application.
Background technology
Propylene glycol is widely used in industries such as printing ink, paint, printing, dyestuff, electronic chemical product and weaving as a kind of hypotoxic senior solvent product, is progressively replacing highly toxic glycol ether, and swift and violent development was arranged in the more than ten years in the past.The industrial propylene oxide method synthesis of propylene glycol of using, promptly synthetic under the effect of catalyst by expoxy propane and lower aliphatic alcohols.Because there is open loop orientation problem in expoxy propane, has two kinds of isomers in the product, 1-alkoxyl-2-propyl alcohol (uncle's ether) and 2-alkoxyl-1-propyl alcohol (secondary ether) are lower according to result of study uncle ether toxicity.
Industrial synthesis of propylene glycol has homogeneous phase method and heterogeneous method, is catalyst with the soda acid generally, and homogeneous acid or base catalyst mainly comprise BF
3, mineral acid and NaOH, sodium alkoxide, potassium alcoholate and tertiary amine, homogeneous catalysis soda acid uniform intensity, catalytic efficiency height, but have problems such as separate complex, equipment corrosion and liquid waste processing, and gradually being eliminated.Solid acid catalyst mainly comprises: cation or hydrogen ion exchange clay, cationic ion-exchange resin and acidic molecular sieve.Be characterized in that catalyst need not separate with product, active and stability is high, some catalyst can the applied catalysis rectification process, and product need not to separate with catalyst, but product isomers uncle's ether and secondary ether ratio are low, and its ratio is generally uncle's ether: secondary ether=75-80: 25-20.Solid base catalyst mainly contains: alkaline water talcum, anion hydrogen oxide clay, anion exchange resin, magnalium complex hydroxide Mg
aAl
h(OH)
2a+3bAnd alkali metal exchange molecular sieve.Be characterized in that catalyst need not separate with product, the isomer products ratio height of uncle's ether and secondary ether, its ratio is uncle's ether: secondary ether=95-97: 5-3, but present activity and stability await further to improve.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can improve product uncle ether and secondary ether isomery ratio, possess the Preparation of catalysts method and the application of high catalytic activity and repeat performance simultaneously.
It is to be active constituent with single-activity center organic solid alkali that catalyst of the present invention is formed, and is carrier with MCM-41, and quaternary ammonium base grafting amount is 0.5-1.5mmol/g.
Aforesaid organic base is TMAH or tetraethyl ammonium hydroxide.
The method for making of catalyst of the present invention comprises the steps:
With r-chloropropyl trimethoxyl silane, cyclohexane and MCM-41 are r-chloropropyl trimethoxyl silane by mass ratio: cyclohexane: MCM-41=5: 30-40: 3-4 mixes, and sealing, after vibrating 1-2 hour under the operating frequency 20-50KHz ultrasonic wave, toluene extracting 8-12 hour, 80-100 ℃ vacuum drying 8-12 hour, get chloropropyl functionalization MCM-41 (Cl/MCM-41), with chloropropyl functionalization MCM-41, quaternary ammonium base and cyclohexane are chloropropyl functionalization MCM-41 by mass ratio: quaternary ammonium base: cyclohexane=3-4: 1-2: 30 mix, and sealing, it was vibrated 1-1.5 hour under operating frequency 20-50KHz ultrasonic wave, toluene extracting 8-12 hour, 80-100 ℃ vacuum drying 8-12 hour, promptly get quaternary ammonium base functionalization MCM-41 catalyst.
Catalyst of the present invention is used for synthesis of propylene glycol, method is to be 2-5 with the mol ratio with methyl alcohol and expoxy propane: 1 ratio, and consumption is that the 1-2% catalyst of reactant gross weight adds in the reactor together, under stirring condition, be warmed up to 100-130 ℃, reacted 5-10 hour, and obtained product through centrifugal sedimentation.
Product analysis: product is analyzed with the GC-920 that sea, Shanghai glad chromatogram Co., Ltd produces.Chromatographic condition is as follows: chromatographic column: external diameter 3mm, the stainless steel column of long 2m; Carrier: GDX-203 (60-80 order); Detector: hydrogen flame; Injector temperature: 220 ℃; The column temperature temperature programming: 100 ℃ of initial temperature, 4 minutes time, 8 ℃/min of heating rate, temperature is 230 ℃ eventually, 10 minutes time; Sample size: 0.1ul.
The present invention compared with prior art has following advantage:
(1) preparation method is simple, and is easy to operate.
(2) in the propylene glycol synthetic reaction, expoxy propane conversion ratio height, reaction condition gentleness, uncle's ether: secondary ether isomery ratio height.
(3) the catalyst repeat performance is good.
The specific embodiment:
Embodiment 1:
The 5.0g r-chloropropyl trimethoxyl silane joined in the 30g cyclohexane dispose solution, ultrasonic wave (operating frequency 50KHz) is uniformly dispersed the back to wherein adding 3.0gMCM-41, and sealing.With this reaction system supersonic oscillations 1 hour.Toluene extracting sample 8 hours, 100 ℃ of vacuum drying 8 hours.Promptly get Cl/MCM-41.Then the 1.0g TMAH is joined in the 30g cyclohexane solution, after ultrasonic wave is uniformly dispersed above-mentioned 3.0g Cl/MCM-41 is immersed wherein, and sealing.With this reaction system supersonic oscillations 0.5 hour.Toluene extracting sample 8 hours, 100 ℃ of vacuum drying 8 hours.Promptly get this catalyst for reaction.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 2: 1, the 2%wt of catalyst amount reactant under the stirring condition, is warming up to 100 ℃, reacted 5 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.The results are shown in Table 1.
Embodiment 2:
The 5.0g r-chloropropyl trimethoxyl silane joined in the 33g cyclohexane dispose solution, ultrasonic wave (operating frequency 40KHz) is uniformly dispersed the back to wherein adding 3.3gMCM-41, and sealing.With this reaction system supersonic oscillations 1.3 hours.Toluene extracting sample 9 hours, 95 ℃ of vacuum drying 9 hours.Promptly get Cl/MCM-41.Then the 1.5g TMAH is joined in the 30g cyclohexane solution, after ultrasonic wave is uniformly dispersed above-mentioned 3.3g Cl/MCM-41 is immersed wherein, and sealing.With this reaction system supersonic oscillations 0.7 hour, toluene extracting sample 9 hours, 90 ℃ of vacuum drying 9 hours.Promptly get this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 3: 1, the 1.6%wt of catalyst amount reactant under the stirring condition, is warming up to 100 ℃, reacted 10 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.The results are shown in Table 1.
Embodiment 3:
The 5.0g r-chloropropyl trimethoxyl silane joined in the 37g cyclohexane dispose solution, ultrasonic wave (operating frequency 28KHz) is uniformly dispersed the back to wherein adding 3.7gMCM-41, and sealing.With this reaction system supersonic oscillations 1.7 hours.Toluene extracting sample 11 hours, 85 ℃ of vacuum drying 11 hours.Promptly get Cl/MCM-41.Then the 1.8g TMAH is joined in the 30g cyclohexane solution, after ultrasonic wave is uniformly dispersed above-mentioned 3.7g Cl/MCM-41 is immersed wherein, and sealing.With this reaction system supersonic oscillations 0.8 hour.Toluene extracting sample 11 hours, 85 ℃ of vacuum drying 11 hours.Get this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 4: 1, the 1.3%wt of catalyst amount reactant under the stirring condition, is warming up to 130 ℃, reacted 5 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.The results are shown in Table 1.
Embodiment 4:
The 5.0g r-chloropropyl trimethoxyl silane joined in the 40g cyclohexane dispose solution, ultrasonic wave (operating frequency 20KHz) is uniformly dispersed the back to wherein adding 4.0gMCM-41, and sealing.With this reaction system supersonic oscillations 2 hours.Toluene extracting sample 12 hours, 80 ℃ of vacuum drying 12 hours.Promptly get Cl/MCM-41.Then the 2.0g TMAH is joined in the 30g cyclohexane solution, after ultrasonic wave is uniformly dispersed above-mentioned 4.0g Cl/MCM-41 is immersed wherein, and sealing.With this reaction system supersonic oscillations 1 hour.Toluene extracting sample 12 hours, 80 ℃ of vacuum drying 12 hours.Get this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 5: 1, the 1.0%wt of catalyst amount reactant under the stirring condition, is warming up to 130 ℃, reacted 10 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.With isolated catalyst detergent drying, standby.The results are shown in Table 1.
Embodiment 5:
The isolated catalyst in embodiment 4 reaction backs is reused as this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 5: 1, the 2%wt of catalyst amount reactant under the stirring condition, is warming up to 130 ℃, reacted 10 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.With isolated catalyst detergent drying, standby.The results are shown in Table 1.
Embodiment 6:
The isolated catalyst in embodiment 5 reaction backs is reused as this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 5: 1, the 2%wt of catalyst amount reactant under the stirring condition, is warming up to 130 ℃, reacted 10 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.With isolated catalyst detergent drying, standby.The results are shown in Table 1.
Embodiment 7:
The isolated catalyst in embodiment 6 reaction backs is reused as this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 5: 1, the 2%wt of catalyst amount reactant under the stirring condition, is warming up to 130 ℃, reacted 10 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.With isolated catalyst detergent drying, standby.The results are shown in Table 1.
Embodiment 8:
The isolated catalyst in embodiment 7 reaction backs is reused as this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 5: 1, the 2%wt of catalyst amount reactant under the stirring condition, is warming up to 130 ℃, reacted 10 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.With isolated catalyst detergent drying, standby.The results are shown in Table 1.
Embodiment 9:
The isolated catalyst in embodiment 8 reaction backs is reused as this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 5: 1, the 2%wt of catalyst amount reactant under the stirring condition, is warming up to 130 ℃, reacted 10 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.The results are shown in Table 1.
Embodiment 10:
The 5.0g r-chloropropyl trimethoxyl silane joined in the 40g cyclohexane dispose solution, ultrasonic wave (operating frequency 20KHz) is uniformly dispersed the back to wherein adding 4.0gMCM-41, and sealing.With this reaction system supersonic oscillations 2 hours.Toluene extracting sample 12 hours, 80 ℃ of vacuum drying 12 hours.Promptly get Cl/MCM-41.Then the 2.0g tetraethyl ammonium hydroxide is joined in the 30g cyclohexane solution, after ultrasonic wave is uniformly dispersed above-mentioned 4.0g Cl/MCM-41 is immersed wherein, and sealing.With this reaction system supersonic oscillations 1 hour.Toluene extracting sample 12 hours, 80 ℃ of vacuum drying 12 hours.Get this catalysts.With methyl alcohol, expoxy propane and catalyst add in the 75ml autoclave, methyl alcohol, expoxy propane mol ratio 5: 1, the 1.0%wt of catalyst amount reactant under the stirring condition, is warming up to 130 ℃, reacted 10 hours, product is got the supernatant gas chromatographic analysis through centrifugal sedimentation.The results are shown in Table 1.
Table 1
| Embodiment | PO conversion ratio (%) | Isomery ratio uncle ether: secondary ether |
| Embodiment 1 | 99.1 | 91.4 |
| Embodiment 2 | 99.3 | 91.2 |
| Embodiment 3 | 99.2 | 90.1 |
| Embodiment 4 | 99.6 | 92.1 |
| Embodiment 5 | 99.5 | 93.0 |
| Embodiment 6 | 99.7 | 92.8 |
| Embodiment 7 | 97.7 | 91.4 |
| Embodiment 8 | 98.9 | 90.8 |
| Embodiment 9 | 97.5 | 90.5 |
| Embodiment 11 | 99.7 | 93.4 |
Claims (4)
1, a kind of organic solid base catalyst for synthesizing propylene glycol ether is characterized in that it is to be active constituent with the quaternary ammonium base that catalyst is formed, and is carrier with MCM-41, and quaternary ammonium base grafting amount is 0.5-1.5mmol/g.
2, a kind of organic solid base catalyst for synthesizing propylene glycol ether as claimed in claim 1 is characterized in that described quaternary ammonium base is TMAH or tetraethyl ammonium hydroxide.
3, the preparation method of a kind of organic solid base catalyst for synthesizing propylene glycol ether as claimed in claim 1 or 2 is characterized in that comprising the steps:
With r-chloropropyl trimethoxyl silane, cyclohexane and MCM-41 are r-chloropropyl trimethoxyl silane by mass ratio: cyclohexane: MCM-41=5: 30-40: 3-4 mixes, and sealing, after vibrating 1-2 hour under the operating frequency 20-50KHz ultrasonic wave, toluene extracting 8-12 hour, 80-100 ℃ vacuum drying 8-12 hour, get chloropropyl functionalization MCM-41, with chloropropyl functionalization MCM-41, quaternary ammonium base and cyclohexane are chloropropyl functionalization MCM-41 by mass ratio: quaternary ammonium base: cyclohexane=3-4: 1-2: 30 mix, and sealing, it was vibrated 1-1.5 hour under operating frequency 20-50KHz ultrasonic wave, toluene extracting 8-12 hour, 80-100 ℃ vacuum drying 8-12 hour, promptly get quaternary ammonium base functionalization MCM-41 catalyst.
4, the application process of a kind of organic solid base catalyst for synthesizing propylene glycol ether as claimed in claim 1 or 2, it is characterized in that with methyl alcohol and expoxy propane be 2-5 with the mol ratio: 1 ratio, and consumption is that the 1-2% catalyst of reactant gross weight adds in the reactor together, under stirring condition, be warmed up to 100-130 ℃, reacted 5-10 hour, and obtained propylene glycol through centrifugal sedimentation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921179A (en) * | 2010-08-11 | 2010-12-22 | 安徽立兴化工有限公司 | Preparation method of dipropylene glycol methyl propyl ether |
| CN103008007A (en) * | 2012-12-10 | 2013-04-03 | 厦门大学 | Resin-type solid base catalyst for synthesis of propylene glycol ether and preparation method and application thereof |
| CN105669390A (en) * | 2016-03-07 | 2016-06-15 | 南京师范大学 | Continuous preparation method of propylene glycol monobutyl ether |
| CN108212196A (en) * | 2018-01-16 | 2018-06-29 | 中国科学院过程工程研究所 | A kind of preparation method and application of the composite catalyst of synthesis of propylene glycol |
-
2005
- 2005-12-01 CN CN 200510048149 patent/CN1775355A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921179A (en) * | 2010-08-11 | 2010-12-22 | 安徽立兴化工有限公司 | Preparation method of dipropylene glycol methyl propyl ether |
| CN101921179B (en) * | 2010-08-11 | 2013-03-27 | 安徽立兴化工有限公司 | Preparation method of dipropylene glycol methyl propyl ether |
| CN103008007A (en) * | 2012-12-10 | 2013-04-03 | 厦门大学 | Resin-type solid base catalyst for synthesis of propylene glycol ether and preparation method and application thereof |
| CN103008007B (en) * | 2012-12-10 | 2014-11-05 | 厦门大学 | Resin-type solid base catalyst for synthesis of propylene glycol ether and preparation method and application thereof |
| CN105669390A (en) * | 2016-03-07 | 2016-06-15 | 南京师范大学 | Continuous preparation method of propylene glycol monobutyl ether |
| CN108212196A (en) * | 2018-01-16 | 2018-06-29 | 中国科学院过程工程研究所 | A kind of preparation method and application of the composite catalyst of synthesis of propylene glycol |
| CN108212196B (en) * | 2018-01-16 | 2020-05-01 | 中国科学院过程工程研究所 | Preparation method and application of composite catalyst for synthesizing propylene glycol ether |
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