CN1033842C - Modified alumina catalyst for producing alkoxyl alcohol - Google Patents
Modified alumina catalyst for producing alkoxyl alcohol Download PDFInfo
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- CN1033842C CN1033842C CN 92113418 CN92113418A CN1033842C CN 1033842 C CN1033842 C CN 1033842C CN 92113418 CN92113418 CN 92113418 CN 92113418 A CN92113418 A CN 92113418A CN 1033842 C CN1033842 C CN 1033842C
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- modified alumina
- alumina catalyst
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- alcohol
- solid
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Abstract
The present invention relates to a solid modified alumina catalyst which has the advantages of simple and convenient preparation method. The present invention can be used for producing alkoxyl alcohol in liquid-solid phase catalytic reaction of C2-C4 oxyalkylene and lower alcohol. The conversion rate of the oxyalkylene can reach 100%, and the selectivity of the mono-alkoxyl alcohol can reach 80% to 98%.
Description
The present invention is used to produce the used modified alumina catalyst of alkoxyl alcohol.Catalyzer of the present invention can make the olefin oxide that contains 2～4 carbon atoms and lower alcohol under liquid-phase condition, and the liquid air speed is not more than at 10 o'clock
-1, alcohol and the mol ratio of olefin oxide be 3～7, temperature of reaction is 90～140 ℃, when reaction pressure is 0.7～1.5 MPa (gauge pressure). can make when carrying out liquid-solid phase catalyzed reaction generation alkoxyl alcohol that the transformation efficiency of olefin oxide is nearly 100%, the selectivity of monoalkoxy alcohol can reach 80～98%.
Alkoxyl alcohol industrial commonly used have glycol ether and propylene glycol.Because they structurally contain two strong solvent borne groups---have the ehter bond and the hydroxyl of alkyl, use so can make the solvent of multiple synthetic resin, fats, dyestuff.Industrially be widely used for coating, printing ink, dyestuff, take pictures, rust-preventive agent, hydraulic efficiency oil, brake solution, frostproofer, lubricant; Also making solvent in industries such as makeup, spices uses.
When synthesizing alkoxyl alcohol, adopted an acidic catalyst, as BF in the past
3, H
2SO
4Except that its side reaction how, catalyzer and product exist in the same liquid phase, thus not easily separated and reclaim excessive alcohol and need add in the alkali and after just can carry out rectification and purification.When adopting basic catalyst, in order to improve the selectivity of monoalkoxy alcohol, the general mol ratio of all liking to adopt higher pure olefin oxide, must recycle and reuse except to unreacted alcohol excess, in reaction process, separate out and form line clogging, make technological operation bring difficulty owing to the crystallisate of alkali.
In order to overcome the shortcoming of above-mentioned industrial production alkoxyl alcohol, solid catalysts such as some solid acids, solid alkali, molecular sieve, ion exchange resin, atlapulgite and composite oxides use in succession in recent years, demonstrate initial activity and selectivity preferably though these catalyzer have, but degenerate through tending to take place activity after the short period of time use, thereby work-ing life is short.Japanese Patent Laid discloses clear 55-149649 and has reported appendix iron family metal elemental nickel on the porousness silica-alumina supports, roasting becomes solid catalyst in 600～1100 ℃ of temperature ranges, overcome above-mentioned activity of such catalysts degenerate problem, but want the appendix metallic element in the catalyst preparation process, and maturing temperature is higher, makes the catalyzer method for making complicated.Catalyzer in use exists the lower problem of selectivity of monoalkoxy alcohol in addition.
Because the pure and mild tri-alkoxy alcohol of dialkoxy is restricted on use range, can overcome the shortcoming of above-mentioned well-known catalyzer in producing alkoxyl alcohol so development is a kind of, can make method for making convenience, the cost of catalyzer low again, and again can highly selective obtaining the solid catalyst of monoalkoxy alcohol, is very important in industrial production.
The present invention is a kind of solid catalyst, is the modified alumina catalyst through special processing.This activity of such catalysts height, the selectivity height of monoalkoxy alcohol; And can be at C
2～C
4Olefin oxide and the reaction of lower alcohol in keep stability for a long time.Solid modified alumina catalyst of the present invention can use in suspension reactor, the reactor of being with stirring and fixed-bed reactor.
Solid modified alumina catalyst of the present invention is characterised in that the aluminium oxide catalyst precursor of making places the acid of 0.1～1N concentration or alkali lye to carry out modification in 4～10 hours in 100～250 ℃ of dippings, wash through water coolant again, the washing water waste liquid requires PH=7, and last drying requirement parches.
The method for making of solid modified alumina catalyst of the present invention is to be the above colloid aluminum oxide of 95% (weight percentage) and with 50～70 gram deionized waters with per 100 gram purity, add an amount of binding agent 3～10 grams, acid 4～10 grams, through the right cylinder of kneading, ordinary methods such as extrusion, pelletizing are shaped to 1.6～2.0 millimeters * 2～4 millimeters of φ, the oven dry back was made catalyst precursor of the present invention in 2～6 hours at 500～700 ℃ of roasting temperatures.With catalyst precursor of the present invention with more than 4 times in the 0.1～1N of its volume acid or alkali lye dip treating 4～10 hours, after cooling off with deionized water wash to the pH value of scrub raffinate be 7, again oven dry the solid modified alumina catalyst.
[embodiment 1] gets 150～160 order β-Al
2O
33H
2O 100 gram, water 60 grams, adhesive starch 8 grams, hydrochloric acid 6 grams (by the concentrated hydrochloric acid conversion), through knead, after the right cylinder oven dry that extrusion, pelletizing become 1.6～2.0 millimeters * 2～4 millimeters of φ in muffle furnace 550 ℃ of roasting temperatures 2 hours.The catalyst precursor 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.Aluminum oxide right cylinder catalyst precursor that will correcting one's mistakes property after the cooling with deionized water wash to the PH=7 of scrub raffinate for extremely.Parch again solid modified alumina catalyst of the present invention.The catalyzer of present embodiment 1 is investigated more than 500 hours in fixed bed continuously, investigates data and sees Table 1.
Get greater than 60 purpose α-Al [embodiment 2]
2O
33H
2O 100 gram, water 60 grams, binding agent sesbania powder 6 grams, nitric acid 8 grams (by the concentrated nitric acid conversion), through the right cylinder of kneading, extrusion, pelletizing become 1.6～2.0 millimeters * 2～4 millimeters of φ, oven dry back 650 ℃ of roasting temperatures 6 hours in muffle furnace.The catalyst precursor 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.Aluminum oxide right cylinder that will correcting one's mistakes property after the cooling with deionized water wash to the PH=7 of scrub raffinate for extremely.Parch again solid modified alumina catalyst of the present invention.The catalyzer of present embodiment 2 is continuously investigated 1500 hours in the fixed bed pipe, investigation the results are shown in Table 1.
Get greater than 60 purpose α-Al [embodiment 3]
2O
33H
2O 100 gram, water 60 grams, binding agent sesbania powder 3 grams, hydrochloric acid 4 grams (by the concentrated hydrochloric acid conversion), through knead, extrusion, pelletizing become 1.6～2.0 millimeters * 2～4 millimeters right cylinders oven dry of φ after in muffle furnace 600 ℃ of roasting temperatures 4 hours.The catalyst precursor that makes is placed a container, add 10 times to the 0.8N of its volume ammonia soln, dipping is 6 hours under 150 ℃ of temperature.Will correcting one's mistakes property aluminum oxide right cylinder after the cooling with deionized water wash to the PH=7 of scrub raffinate for extremely.Parch again and promptly become solid modified alumina catalyst of the present invention.The catalyzer of present embodiment 3 is continuously investigated 500 hours in fixed bed, investigation the results are shown in Table 1.
[comparative example] got greater than 60 purpose α-Al
2O
33H
2O 100 gram, water 60 grams, binding agent sesbania powder 3 grams, nitric acid 2 grams (by the concentrated nitric acid conversion), through the right cylinder of kneading, extrusion, pelletizing become 1.6～2.0 millimeters * 2～4 millimeters of φ, oven dry back 600 ℃ of roasting temperatures 4 hours in muffle furnace.Not carrying out modification handles.In fixed bed, investigate 500 hours continuously, investigate and the results are shown in Table 1.
3 tie up to long 90 centimetres, φ 12 * 2 from the little anti-investigation of rice in the investigation process in comparative example and embodiment 1, surplusly all investigate at long 4 meters, 25 * 2.5 centimetres of single tubes of φ, the pipe material is stainless steel.
Table 1
| Example | Raw material | Alcohol/olefin oxide mol ratio | Liquid air speed hour | Temperature of reaction ℃ | The reaction pressure MPa | Olefin oxide transformation efficiency % | Monoalkoxy alcohol selectivity % | Dialkoxy alcohol selectivity % | ||
| Embodiment 1 | 1 2 3 | Oxyethane propylene oxide propylene oxide | The methyl alcohol methanol | 7 7 7 | 6.5 7.0 7.0 | 115 115 120 | 1.5 1.5 0.8 | 100 100 100 | 92.1 93.4 90.5 | 7.0 5.3 6.1 |
| Embodiment 2 | 4 5 6 | Propylene oxide propylene oxide propylene oxide | The methanol butanols | 5 5 5 | 5.0 5.0 5.0 | 115 120 125 | 1.5 1.5 1.5 | 100 100 100 | 97.2 91.6 83.2 | 1.8 5.5 12.5 |
| Embodiment 3 | 7 8 9 | Propylene oxide propylene oxide propylene oxide | The methanol butanols | 5 5 5 | 5.0 5.0 5.0 | 115 120 125 | 1.5 1.5 1.5 | 100 100 100 | 95.2 90.2 81.0 | 3.5 8.1 1 |
| Comparative example | 10 11 | The propylene oxide propylene oxide | Ethanol methyl alcohol | 7 7 | 8.5 8.5 | 115 110 | 0.8 0.8 | 96.1 95.9 | 73.0 82.0 | |
Claims (3)
1, a kind of solid modified alumina catalyst that is applicable to the liquid-solid state reaction of producing alkoxyl alcohol, it is characterized in that the precursor of the good aluminum oxide right cylinder of shaping and roasting as catalyzer, placing volume is the acid solution or the alkali lye of its 0.1～1N concentration of 4 times, carried out modification in 4～10 hours at 100～250 ℃ of dippings, catalyst precursor after the modification washs to scrub raffinate PH=7 with deionized water, again oven dry.
2, the solid modified alumina catalyst that is applicable to the liquid-solid state reaction of producing alkoxyl alcohol according to claim 1 is characterized in that maturing temperature is 500～700 ℃, and roasting time is 2～6 hours.
3, the solid modified alumina catalyst that is applicable to the liquid-solid state reaction of producing alkoxyl alcohol according to claim 1 is characterized in that used acid is hydrochloric acid, phosphoric acid, formic acid, acetate; Used alkali is ammoniacal liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92113418 CN1033842C (en) | 1992-11-24 | 1992-11-24 | Modified alumina catalyst for producing alkoxyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92113418 CN1033842C (en) | 1992-11-24 | 1992-11-24 | Modified alumina catalyst for producing alkoxyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1087288A CN1087288A (en) | 1994-06-01 |
| CN1033842C true CN1033842C (en) | 1997-01-22 |
Family
ID=4946391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92113418 Expired - Fee Related CN1033842C (en) | 1992-11-24 | 1992-11-24 | Modified alumina catalyst for producing alkoxyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033842C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063099C (en) * | 1996-10-22 | 2001-03-14 | 中国石油化工总公司上海石油化工研究院 | Catalyzer for preparing propylene-glycol ether |
| CN102633611B (en) * | 2012-03-28 | 2014-04-16 | 南开大学 | Method of using modified alumina catalyst to continuously prepare methyl vinyl ketone |
| CN106748679A (en) * | 2016-11-23 | 2017-05-31 | 山东玉皇化工有限公司 | A kind of method for catalyzing and synthesizing propylene glycol monomethyl ether |
-
1992
- 1992-11-24 CN CN 92113418 patent/CN1033842C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1087288A (en) | 1994-06-01 |
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|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 19970122 Termination date: 20091224 |