CN1063099C - Catalyzer for preparing propylene-glycol ether - Google Patents
Catalyzer for preparing propylene-glycol ether Download PDFInfo
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- CN1063099C CN1063099C CN96116546A CN96116546A CN1063099C CN 1063099 C CN1063099 C CN 1063099C CN 96116546 A CN96116546 A CN 96116546A CN 96116546 A CN96116546 A CN 96116546A CN 1063099 C CN1063099 C CN 1063099C
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- ether
- catalyst
- propylene glycol
- alkali metal
- aluminium oxide
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Abstract
The present invention relates to a catalyst used for preparing propanediol ether. Firstly, hole expanding modification is carried out for aluminum oxide with acid or alkaline liquor; then, 5 to 4 wt% of alkali metal fluoride is used for dipping. The prepared catalyst used for preparing propylene-glycol ether has the characteristics of higher reactive yield and the higher molar ratio of propanediol primary ether to propanediol secondary ether of two isomers, and the molar ratio can reach 95.1:4.9. The present invention is suitable for being used in industrial production.
Description
The present invention relates to be used to prepare the catalyst of propylene glycol, particularly about being used to prepare the modified alumina catalyst of propylene glycol.
Propylene glycol mainly is to be that raw material reaction makes with expoxy propane and lower aliphatic alcohols.Owing to contain ehter bond and two kinds of groups of hydroxyl in its structure, therefore the propylene glycol product is good industrial solvent, can be widely used in coating, printing, dyestuff, cleaning agent, printing ink, photograph, antirust agent, hydraulic oil, brake fluid, antifreezing agent, the lubricant.Also making solvent in industries such as cosmetics, spices uses.Propylene glycol can be divided into propane diols uncle's ether and the secondary ether of propane diols according to the residing position of its hydroxyl.The glycol ethers product toxicological study report of delivering according to European chemical industry toxicity center shows: propane diols uncle ether is littler several times than the toxicity of the secondary ether of propane diols, so in the propylene glycol product, contains the index that more propane diols uncle ether has become people to pursue.The catalyst of industrial in the past production propylene glycol is used sodium alkoxide (potassium), boron trifluoride always.The technical process of these catalyst exists problems such as flow process complexity, yield are not high, catalyst needs neutralisation treatment, quantity of three wastes is more, equipment corrosion is serious.Document Chinese patent 92113418.5 discloses a kind ofly makes catalyst with modified aluminas, carries out liquid and solid phase reaction, and the pressurization successive reaction is produced propylene glycol, and the expoxy propane conversion ratio is greater than 98.5%, and the monoether yield is greater than 92%.But the mol ratio of uncle's ether of the propane diols in the production propylene glycol and the secondary ether of propane diols is 3: 1, and the growing amount of the secondary ether of propane diols that toxicity is bigger is bigger, influences the quality and the class of product.
The purpose of this invention is to provide a kind of catalyst that is used to prepare propylene glycol, this catalyst is used for the expoxy propane etherification technology, both had higher reaction yield, it is higher with the mol ratio of the propane diols ether second month in a season to generate in two isomers of propylene glycol propane diols uncle ether simultaneously.
The objective of the invention is to realize by following technical scheme: a kind of catalyst that is used to prepare propylene glycol comprises component alkali metal fluoride 5～40%, aluminium oxide 60～95% by weight percentage.
The amount preferable range of alkali metal fluoride is 15～30% in the technique scheme, and described propylene glycol is meant propylene glycol monomethyl ether, propylene-glycol ethyl ether, propane diols butyl ether.Aluminium oxide is a gama-alumina, and alkali metal fluoride is cesium fluoride or potassium fluoride.Aluminium oxide is with handling in the 0.1～1N of its volume acid or alkali lye more than 4 times.
Catalyst of the present invention is to make by following method: with per 100 gram purity is above colloid aluminium oxide of 95% (weight) and 160～170 gram deionized waters, add an amount of binding agent 3～10 grams, acid 4～10 restrains, and is shaped to the cylinder of 1.6～2.0 millimeters * 2～4 millimeters of φ through conventional methods such as kneading, extrusion, pelletizings.The oven dry back is under 500～700 ℃ of temperature, and this catalyst precarsor was made in roasting in 2～6 hours.With catalyst precarsor of the present invention with more than 4 times in the 0.1～1N of its volume acid or alkali lye impregnation process 4～10 hours, after cooling off with deionized water wash to the pH value of scrub raffinate be 7, after the oven dry, promptly get the catalyst that is used to prepare propylene glycol again with infusion process dipping alkali metal fluoride 5～40% (percentage by weight).
The present invention makes the hydroxylating surface of fluorine ion and aluminium oxide form strong hydrogen bond owing to flooded 5～40% alkali metal fluoride on modified aluminas, causes weakening of fluorine ion nucleophilicity, produces the center of negative charge of local dense simultaneously.And because the high degree of dispersion of alkali metal fluoride, make alumina surface have the undersaturated fluorine ion of complexing, all make alkali metal fluoride-aluminium oxide have strong alkalescence, thereby make this system be used for expoxy propane etherificate when reaction, can improve the selectivity of generation propane diols primary ether.Propane diols uncle ether in the product: the secondary ether mol ratio of propane diols can reach 19: 1, promptly 95%: 5%.
The invention will be further elaborated below by embodiment.[embodiment 1]
Get 150～160 order β-Al
2O
33H
2O100 gram, water 60 grams, adhesive starch 8 grams, hydrochloric acid 6 grams (by the concentrated hydrochloric acid conversion) become after the cylinder oven dry of 1.6～2.0 millimeters * 2～4 millimeters of φ in muffle furnace 550 ℃ of roasting temperatures 2 hours through kneading, extrusion, pelletizing.The catalyst precarsor that makes is placed a container, add 4 times to the 0.4N of its volume phosphoric acid solution, dipping is 4 hours under 150 ℃ of temperature.After the cooling aluminium oxide cylinder catalyst precarsor of modification is washed till the PH=7 of scrub raffinate with deionized water.Parch again solid modified aluminas of the present invention.Solid modified aluminas with making floods potassium fluoride with infusion process, makes catalyst required for the present invention, fluorinated potassium 15% by weight percentage in the catalyst, and aluminium oxide is 85%.The catalyst of present embodiment 1 is investigated evaluation in fixed bed, appreciation condition is: the mol ratio of material benzenemethanol/expoxy propane is 5: 1, and bed liquid air speed is 5.0 hours
-1, reaction temperature is 115 ℃, reaction pressure is 1.5MPa.Reaction result is: the conversion ratio of expoxy propane is 95.3%, and the selectivity of propylene glycol monomethyl ether is 98.4%, and wherein the mol ratio of two of propylene glycol monomethyl ether isomers uncle ether/secondary ethers is 94.5: 5.5.[embodiment 2]
According to each step of embodiment 1, fluorinated potassium 30% by weight percentage in the catalyst just, aluminium oxide is 70%.Reaction raw materials is that the mol ratio of ethanol/expoxy propane is 5: 1, and bed liquid air speed is 5.0 hours
-1, reaction temperature is 120 ℃, reaction pressure is 1.5MPa.Reaction result is: the conversion ratio of expoxy propane is 96.6%, and the selectivity of propylene-glycol ethyl ether is 93.8%, and wherein the mol ratio of two of propylene-glycol ethyl ether isomers uncle ether/secondary ethers is 95.0: 5.0.[embodiment 3]
Get greater than 60 purpose α-Al
2O
33H
2O100 gram, water 60 grams, binding agent sesbania powder 6 grams, nitric acid 8 grams (by the red fuming nitric acid (RFNA) conversion) become the cylinder of 1.6～2.0 millimeters * 2～4 millimeters of φ through kneading, extrusion, pelletizing, oven dry back 650 ℃ of roasting temperatures 6 hours in muffle furnace.The catalyst precarsor that makes is placed a container, add 6 times to the 0.5N of its volume formic acid solution, dipping is 10 hours under 125 ℃ of temperature.Aluminium oxide cylinder that will correcting one's mistakes property after the cooling washs till the PH=7 of scrub raffinate with deionized water.Parch again solid modified alumina catalyst of the present invention.Solid modified aluminas with making floods potassium fluoride with infusion process, makes catalyst required for the present invention, fluorinated potassium 28% by weight percentage in the catalyst, aluminium oxide 72%.The catalyst of present embodiment 3 is investigated evaluation in fixed bed, appreciation condition is: the mol ratio of material benzenemethanol/expoxy propane is 5: 1, and bed liquid air speed is 5.0 hours
-1, reaction temperature is 115 ℃, reaction pressure is 1.5MPa.Reaction result is: the conversion ratio of expoxy propane is 95.7%, and the selectivity of propylene glycol monomethyl ether is 99.01%, and wherein the mol ratio of two of propylene glycol monomethyl ether isomers uncle ether/secondary ethers is 95.1: 4.9.[embodiment 4]
According to each step of embodiment 3, what just flood in the solid modified aluminas is cesium fluoride, by weight percentage, and fluorinated caesium 5% in the catalyst, aluminium oxide 95%.Reaction raw materials and appreciation condition are also with embodiment 3, and last reaction result is: the conversion ratio of expoxy propane is 92.8%, and the selectivity of propylene glycol monomethyl ether is 96.7%, and wherein the mol ratio of two of propylene glycol monomethyl ether isomers uncle ether/secondary ethers is 93.3: 6.7.[embodiment 5]
Get greater than 60 purpose α-Al
2O
33H
2O100 gram, water 60 grams, binding agent sesbania powder 3 grams, hydrochloric acid 4 grams (by the concentrated hydrochloric acid conversion) become the cylinder of 1.6～2.0 millimeters * 2～4 millimeters of φ through kneading, extrusion, pelletizing, oven dry back 600 ℃ of roasting temperatures 4 hours in muffle furnace.The catalyst precarsor that makes is placed a container, add 10 times to the 0.8N of its volume ammonia spirit, dipping is 6 hours under 150 ℃ of temperature.Aluminium oxide cylinder that will correcting one's mistakes property after the cooling washs till the PH=7 of scrub raffinate with deionized water.Parch again solid modified alumina catalyst of the present invention.Solid modified aluminas with making floods potassium fluoride with infusion process, makes catalyst required for the present invention, fluorinated potassium 40% by weight percentage in the catalyst, aluminium oxide 60%.The catalyst of present embodiment is investigated evaluation in fixed bed, appreciation condition is: the mol ratio of raw material butanols/expoxy propane is 5: 1, and bed liquid air speed is 5.0 hours
-1, reaction temperature is 125 ℃, reaction pressure is 1.5MPa.Reaction result is: the conversion ratio of expoxy propane is 97.9%, and the selectivity of propane diols butyl ether is 88.50%, and wherein the mol ratio of two of the propane diols butyl ether isomers uncle ether/secondary ethers is 92.9: 7.1.[comparative example 1]
Step by embodiment 1 is prepared into the solid modified aluminas.This aluminium oxide is investigated evaluation as catalyst in fixed bed, appreciation condition is: the mol ratio of material benzenemethanol/expoxy propane is 5: 1, and bed liquid air speed is 5.0 hours
-1, reaction temperature is 115 ℃, reaction pressure is 1.5MPa.Reaction result is: the conversion ratio of expoxy propane is 100%, and the selectivity of propylene glycol monomethyl ether is 97.2%, and wherein the mol ratio of two of propylene glycol monomethyl ether isomers uncle ether/secondary ethers is 75: 25.
Claims (4)
1, a kind of catalyst that is used to prepare propylene glycol is characterized in that comprising by weight percentage component alkali metal fluoride 5～40%, gama-alumina 60～95%.
2,, it is characterized in that alkali metal fluoride is 15～30% by weight percentage according to the described catalyst that is used to prepare propylene glycol of claim 1.
3,, it is characterized in that alkali metal fluoride is cesium fluoride or potassium fluoride according to the described catalyst that is used to prepare propylene glycol of claim 1.
4,, it is characterized in that aluminium oxide is with handling in the 0.1～1N of its volume acid or alkali lye more than 4 times according to the described catalyst that is used to prepare propylene glycol of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116546A CN1063099C (en) | 1996-10-22 | 1996-10-22 | Catalyzer for preparing propylene-glycol ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116546A CN1063099C (en) | 1996-10-22 | 1996-10-22 | Catalyzer for preparing propylene-glycol ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1180585A CN1180585A (en) | 1998-05-06 |
| CN1063099C true CN1063099C (en) | 2001-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116546A Expired - Lifetime CN1063099C (en) | 1996-10-22 | 1996-10-22 | Catalyzer for preparing propylene-glycol ether |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100386145C (en) * | 2006-06-07 | 2008-05-07 | 山东轻工业学院 | Solid catalyst for synthesizing propylene glycol ether and its preparing process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297415A (en) * | 1987-05-29 | 1988-12-05 | Mitsui Toatsu Chem Inc | Production of heat-resistant polymer |
| EP0421677A1 (en) * | 1989-10-04 | 1991-04-10 | The British Petroleum Company P.L.C. | Process for the preparation of glycol ethers |
| US5110991A (en) * | 1991-04-01 | 1992-05-05 | Texaco Chemical Company | Heterogeneous catalyst for alkoxylation of alcohols |
| WO1992011224A1 (en) * | 1990-12-20 | 1992-07-09 | The British Petroleum Company Plc | Process for the preparation of glycol ethers |
| CN1087288A (en) * | 1992-11-24 | 1994-06-01 | 中国石油化工总公司上海石油化工研究院 | Be used to produce the modified alumina catalyst of alkoxyl alcohol |
-
1996
- 1996-10-22 CN CN96116546A patent/CN1063099C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297415A (en) * | 1987-05-29 | 1988-12-05 | Mitsui Toatsu Chem Inc | Production of heat-resistant polymer |
| EP0421677A1 (en) * | 1989-10-04 | 1991-04-10 | The British Petroleum Company P.L.C. | Process for the preparation of glycol ethers |
| WO1992011224A1 (en) * | 1990-12-20 | 1992-07-09 | The British Petroleum Company Plc | Process for the preparation of glycol ethers |
| US5110991A (en) * | 1991-04-01 | 1992-05-05 | Texaco Chemical Company | Heterogeneous catalyst for alkoxylation of alcohols |
| CN1087288A (en) * | 1992-11-24 | 1994-06-01 | 中国石油化工总公司上海石油化工研究院 | Be used to produce the modified alumina catalyst of alkoxyl alcohol |
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| Publication number | Publication date |
|---|---|
| CN1180585A (en) | 1998-05-06 |
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