CN1288121C - Solid catalyst for synthesizing propylene glycol ether, its preparing process and use thereof - Google Patents
Solid catalyst for synthesizing propylene glycol ether, its preparing process and use thereof Download PDFInfo
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- CN1288121C CN1288121C CN 200310109694 CN200310109694A CN1288121C CN 1288121 C CN1288121 C CN 1288121C CN 200310109694 CN200310109694 CN 200310109694 CN 200310109694 A CN200310109694 A CN 200310109694A CN 1288121 C CN1288121 C CN 1288121C
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Abstract
The present invention relates to a solid catalyst for synthesizing propylene glycol ether, which is a ZnO/active carbon catalyst by immersing active carbon with the water solution of zinc nitrate and zinc acetate and is dried at 110 DEG C for 12 hours and calcined in nitrogen gas at 400 DEG C to 600 DEG C for 4 hours. The catalyst has the advantages of simple preparation method, easy operation, and little pollution by carbon dioxide and water in the air. Simultaneously, the catalyst has the characteristics of high conversion rate of propylene oxide, high isomerization proportion of primary ethers to secondary ethers, high selectivity of propylene glycol ether, etc.
Description
Technical field
The invention belongs to a kind of solid catalyst and method for making and application, relate in particular to a kind of solid catalyst and method for making and application that is used for the propylene oxide method synthesis of propylene glycol.
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 catalyzer by propylene oxide and lower aliphatic alcohols.Because there is open loop orientation problem in propylene oxide, has two kinds of isomer in the product, 1-alkoxyl group-2-propyl alcohol (uncle's ether) and 2-alkoxyl group-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 catalyzer with the soda acid generally, and homogeneous acid or alkaline catalysts 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 disposal, and gradually being eliminated.Solid acid catalyst mainly comprises: positively charged ion or hydrogen ion exchange clay, Zeo-karb and acidic molecular sieve.Be characterized in that catalyzer need not separate with product, active and stability is high, some catalyzer can the applied catalysis rectification process, and product need not to separate with catalyzer, but product isomer 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 compound clay, anionite-exchange resin, magnalium complex hydroxide Mg
aAl
b(OH)
2a+3bAnd basic metal exchange molecular sieve.Be characterized in that catalyzer 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 a kind of product uncle ether that can improve in secondary ether isomery ratio, possess high catalytic activity catalyst and preparation method and application simultaneously.
The weight percentage of consisting of of catalyzer of the present invention: ZnO is 10-70%, and the weight percentage of gac is 90-30%.
Aforesaid gac is coconut husk, ature of coal type, and specific surface is 400～1000m
2/ g.
The method for making of catalyzer of the present invention comprises the steps
(1) gac at first in nitrogen 500-1000 ℃ handled 1 hour;
(2) zinc nitrate or zinc acetate are made into the 10-50% aqueous solution, dipping coconut husk type or ature of coal type gac 12 hours;
(3) 110 ℃ of oven dry 12 hours, under nitrogen protection, temperature is risen to 400-600 ℃ with the temperature rise rate of 5-15 ℃/Min, constant temperature 2-6 hour, reduce to room temperature and promptly get catalyzer.
Catalyzer of the present invention is used for synthesis of propylene glycol, method is to be 3-7 with the mol ratio with methyl alcohol and propylene oxide: 1 ratio, add in the reactor together with 0.5～4% catalyzer of reactant gross weight, under agitation condition, be warmed up to 80～140 ℃, reacted 2～5 hours, and obtained product through centrifugal settling.
Product analysis: reaction product is analyzed with the GC-920 that sea, Shanghai glad chromatogram company limited 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; Sampler temperature: 220 ℃; The column temperature temperature programming: 100 ℃ of initial temperature, 4 minutes time, 8 ℃/min of temperature rise 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 building-up reactions, propylene oxide transformation efficiency height, reaction conditions gentleness, uncle's ether: secondary ether isomery ratio height.
3) propylene glycol selectivity height
4) cost is low, and catalyzer is difficult for by airborne CO
2, H
2O pollutes.
Embodiment:
Embodiment 1:
With 1.21g Zn (NO
3)
26H
2O is dissolved in the 3ml deionized water, and the coconut husk type gac (80-100 order) of 750 ℃ of roastings of dipping 3g 12 hours in 110 ℃ of oven dry 12 hours, is that 10 ℃/min rises to 600C with temperature rise rate, and constant temperature 4 hours gets this catalysts.With methyl alcohol, propylene oxide and catalyzer add in the 75ml autoclave, methyl alcohol, propylene oxide mol ratio 5: 1, the 2%wt of catalyst levels reactant under the agitation condition, is warming up to 100 ℃, reacted 5 hours, product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Embodiment 2:
With 4.70g Zn (NO
3)
26H
2O is dissolved in the 5ml deionized water, and dipping 3g 850 ℃ of roasting coconut husks type gac (80-100 order) 12 hours in 110 ℃ of oven dry 12 hours, is that 10 ℃/min rises to 600 ℃ with temperature rise rate, and constant temperature 4 hours gets this catalysts.With methyl alcohol, propylene oxide and catalyzer add in the 75ml autoclave, methyl alcohol, propylene oxide mol ratio 5: 1, the 2%wt of catalyst levels reactant under the agitation condition, is warming up to 100 ℃, reacted 5 hours, product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Embodiment 3:
With 10.97g Zn (NO
3)
26H
2O is dissolved in the 7ml deionized water, and the coconut husk type gac (80-100 order) of 1000 ℃ of roastings of dipping 3g 12 hours in 110 ℃ of oven dry 12 hours, is that 10 ℃/min rises to 600 ℃ with temperature rise rate, and constant temperature 4 hours gets this catalysts.With methyl alcohol, propylene oxide and catalyzer add in the 75ml autoclave, methyl alcohol, propylene oxide mol ratio 5: 1, the 2%wt of catalyst levels reactant under the agitation condition, is warming up to 100 ℃, reacted 3 hours, product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Embodiment 4:
With 25.60g Zn (NO
3)
26H
2O is dissolved in the 14ml deionized water, and the coconut husk type gac (80-100 order) of 500 ℃ of roastings of dipping 3g 12 hours in 110 ℃ of oven dry 12 hours, is that 10 ℃/min rises to 600 ℃ with temperature rise rate, and constant temperature 4 hours gets this catalysts.With methyl alcohol, propylene oxide and catalyzer add in the 75ml autoclave, methyl alcohol, propylene oxide mol ratio 5: 1, the 2%wt of catalyst levels reactant under the agitation condition, is warming up to 120 ℃, reacted 3 hours, product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Embodiment 5:
With 10.97g Zn (NO
3)
26H
2O is dissolved in the 7ml deionized water, and dipping 3g 700 ℃ of roasting atures of coal type gac (80-100 order) 12 hours in 110 ℃ of oven dry 12 hours, is that 10 ℃/min rises to 600 ℃ with temperature rise rate, and constant temperature 4 hours gets this catalysts.With methyl alcohol, propylene oxide and catalyzer add in the 75ml autoclave, methyl alcohol, propylene oxide mol ratio 5: 1, the 2%wt of catalyst levels reactant under the agitation condition, is warming up to 100 ℃, reacted 5 hours, product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Embodiment 6:
With 25.60g Zn (NO
3)
26H
2O is dissolved in the 14ml deionized water, and the ature of coal type gac (80-100 order) of 900 ℃ of roastings of dipping 3g 12 hours in 110 ℃ of oven dry 12 hours, is that 10 ℃/min rises to 600 ℃ with temperature rise rate, and constant temperature 4 hours gets this catalysts.With methyl alcohol, propylene oxide and catalyzer add in the 75ml autoclave, methyl alcohol, propylene oxide mol ratio 5: 1, the 2%wt of catalyst levels reactant under the agitation condition, is warming up to 120 ℃, reacted 3 hours, product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Embodiment 7:
With 3.47g Zn (CH
3COO)
22H
2O is dissolved in the 5ml deionized water, and the coconut husk type gac (80-100 order) of 850 ℃ of roastings of dipping 3g 12 hours in 110 ℃ of oven dry 12 hours, is that 10 ℃/min rises to 600 ℃ with temperature rise rate, and constant temperature 4 hours gets this catalysts.With methyl alcohol, propylene oxide and catalyzer add in the 75ml autoclave, methyl alcohol, propylene oxide mol ratio 5: 1, the 2%wt of catalyst levels reactant under the agitation condition, is warming up to 100 ℃, reacted 5 hours, product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Embodiment 8:
With 8.09g Zn (CH3COO)
22H
2O is dissolved in the 10ml deionized water, and the coconut husk type gac (80-100 order) of 750 ℃ of roastings of dipping 3g 12 hours in 110 ℃ of oven dry 12 hours, is that 10 ℃/min rises to 600 ℃ with temperature rise rate, and constant temperature 4 hours gets this catalysts.With methyl alcohol, propylene oxide and catalyzer add in the 75ml autoclave, methyl alcohol, propylene oxide mol ratio 5: 1, the 2%wt of catalyst levels reactant under the agitation condition, is warming up to 120 ℃, reacted 5 hours, product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Comparative Examples 1:
Commercial γ-Al with reactant 2%wt
2O
3And methyl alcohol, propylene oxide adds in the 75ml autoclave, methyl alcohol, and propylene oxide mol ratio 5: 1 under the agitation condition, is warming up to 120 ℃, reacts 5 hours, and product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Comparative Examples 2:
With 93.78gAl (NO
3)
39H
2O and 192.3g Mg (NO
3)
26H
2O is made into the 670ml water solution A; Again with 90g NaOH and 70.70g Na
2CO
3Be made into the 670ml solution B.With A solution, B solution and drip are added to together with the flow velocity of 10ml/min, stirring at room, and 60 ℃ of ageings 12 hours are filtered, and wash to filtrate PH=7, and 60 ℃ of dryings 24 hours make hydrotalcite.With hydrotalcite and the methyl alcohol of reactant 2%wt, propylene oxide adds in the 75ml autoclave, methyl alcohol, and propylene oxide mol ratio 5: 1 under the agitation condition, is warming up to 120 ℃, reacts 5 hours, and product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.The results are shown in Table 1.
Table 1
| Embodiment | PO transformation efficiency (%) | Propylene glycol monomethyl ether selectivity (%) | Isomery ratio uncle ether: secondary ether |
| Embodiment 1 | 93.27 | 98.46 | 96.21∶3.79 |
| Embodiment 2 | 96.53 | 98.87 | 97.25∶2.75 |
| Embodiment 3 | 93.17 | 98.24 | 97.36∶2.64 |
| Embodiment 4 | 98.59 | 98.78 | 97.48∶2.52 |
| Embodiment 5 | 95.37 | 98.26 | 98.31∶1.69 |
| Embodiment 6 | 98.16 | 98.85 | 98.43∶1.57 |
| Embodiment 7 | 96.48 | 98.57 | 98.76∶1.24 |
| Embodiment 8 | 99.58 | 98.62 | 98.39∶1.61 |
| Comparative Examples 1 | 99.87 | 94.03 | 73.83∶26.17 |
| Comparative Examples 2 | 71.22 | 96.28 | 85.21∶14.79 |
Claims (4)
1, a kind of solid catalyst of synthesis of propylene glycol, the weight percentage that it is characterized in that ZnO is 10-70%, the weight percentage of gac is 90-30%;
Gac before loading ZnO, earlier in nitrogen 500-1000 ℃ handled 1 hour.
2, the solid catalyst of a kind of synthesis of propylene glycol as claimed in claim 1 is characterized in that described gac is coconut husk or ature of coal type, and specific surface is 400-1000m
2/ g.
3, the preparation method of the solid catalyst of a kind of synthesis of propylene glycol as claimed in claim 1 or 2 is characterized in that comprising the steps:
(1) gac at first in nitrogen 500-1000 ℃ handled 1 hour;
(2) zinc nitrate or zinc acetate are made into the 10-50% aqueous solution, dipping coconut husk type or ature of coal type gac 12 hours;
(3) 110 ℃ of oven dry 12 hours, under nitrogen protection, temperature is risen to 400-600 ℃ with the temperature rise rate of 5-15 ℃/Min, constant temperature 2-6 hour, reduce to room temperature and promptly get catalyzer.
4, the application of the solid catalyst of a kind of synthesis of propylene glycol as claimed in claim 1 or 2, it is characterized in that being is 3-7 with the mol ratio with methyl alcohol and propylene oxide: 1 ratio, add in the reactor together with the 0.5-4% catalyzer of reactant gross weight, under agitation condition, be warmed up to 80-140 ℃, reacted 2-5 hour, and obtained product through centrifugal settling.
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|---|---|---|---|
| CN 200310109694 CN1288121C (en) | 2003-12-11 | 2003-12-11 | Solid catalyst for synthesizing propylene glycol ether, its preparing process and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109694 CN1288121C (en) | 2003-12-11 | 2003-12-11 | Solid catalyst for synthesizing propylene glycol ether, its preparing process and use thereof |
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|---|---|
| CN1546227A CN1546227A (en) | 2004-11-17 |
| CN1288121C true CN1288121C (en) | 2006-12-06 |
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|---|---|---|---|
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| CN111250099B (en) * | 2020-03-31 | 2021-05-07 | 中国科学院过程工程研究所 | Preparation method and application of composite metal oxide catalyst |
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2003
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Granted publication date: 20061206 Termination date: 20171211 |