CN101774898B - Preparation method of acetone alcohol - Google Patents
Preparation method of acetone alcohol Download PDFInfo
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- CN101774898B CN101774898B CN2009100769501A CN200910076950A CN101774898B CN 101774898 B CN101774898 B CN 101774898B CN 2009100769501 A CN2009100769501 A CN 2009100769501A CN 200910076950 A CN200910076950 A CN 200910076950A CN 101774898 B CN101774898 B CN 101774898B
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- ucar
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- hydroxyacetone
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Abstract
The invention relates to a method for preparing acetone alcohol by gas phase dehydrogenation of 1,2-propanediol. The method is used for generating the acetone alcohol by gas phase dehydrogenation of the 1,2-propanediol by using alkali-earth oxides as catalysts. The conversion per pass of the 1,2-propanediol is greater than 60%, and the selectivity of the acetone alcohol in products is greater than 90wt%. The method has the advantages of simple process, low cost and no pollution, and is an environment-friendly acetone alcohol production line.
Description
Technical field
The present invention relates to a kind ofly with 1, the 2-Ucar 35 is the method for feedstock production hydroxyacetone.Particularly, be to be catalyzer with the alkaline earth metal oxide, 1, the dehydrogenation of 2-Ucar 35 catalyzed gas generates the method for hydroxyacetone.
Background technology
Hydroxyacetone has another name called 1-hydroxyl-2-acetone (pyruvic alcohol) or acetylcarbinol, is used for the H of synthetic Digestive tract
2Midbody (s)-(+)-2-aminopropanol of the midbody 4-methylimidazole of blocade Cimitidine Type A/AB, Comprecin RWJ 25213-097, the midbody 4-hydroxy methylimidazole of racemize Histidine; Medicine and the chiral intermediates (1)-(-)-1 such as antipyretic and analgesic Frosst) acetone ester that also are used for vitamin H (vitamin H) and do not have the ulcer toxic side effect, 2-Ucar 35 synthetic.The compound method of hydroxyacetone mainly is: a martonite esterification/alcoholysis method and 1, the oxygen of 2-Ucar 35 or K
2CrO
7/ H
2SO
4Oxidation style etc.The former reaction conditions is gentle, synthetic or the production unit requirement is low and simple, and the product yield high purity is high, is the disadvantage of this method but the price of main raw material one martonite causes production cost too high; Latter reaction's condition and equipment requirements are high, and product yield is low.CN 101016234A provides that a kind of by product is few, technology is simple 1, and the method for 2-Ucar 35 gaseous oxidation coproduction 1-hydroxyl-2-acetone and pyruvic aldehyde, but its catalyzer is an electrolytic silver, costs an arm and a leg at the preparation difficulty.
Summary of the invention
The object of the present invention is to provide a kind ofly 1, the dehydrogenation of 2-Ucar 35 catalyzed gas prepares the method for hydroxyacetone.
For realizing above-mentioned purpose, it is catalyzer that the present invention adopts alkaline earth metal oxide, and with 1, the 2-Ucar 35 is the feedstock production hydroxyacetone, and products distribution is simple, 1, and 2-Ucar 35 transformation efficiency is higher, and the hydroxyacetone selectivity is high.
Catalyzer of the present invention is the alkaline earth metal oxide catalyzer, and earth alkali metal is one or more the mixture in magnesium, calcium, strontium and the barium.
Catalyst preparation step of the present invention is following:
(1) by the soluble salt solution of earth alkali metal and sodium hydroxide, Pottasium Hydroxide or yellow soda ash, wet chemical in room temperature-100 ℃ reaction down, ageing 1-10 hour, generate oxyhydroxide or subcarbonate, the carbonate sediment of earth alkali metal;
(2) throw out that step 1 is obtained separates, drying, obtains oxyhydroxide or subcarbonate, the carbonate solid of earth alkali metal;
(3) solid that step 2 is obtained made catalyst sample at 500-1000 ℃ of following roasting 3-6 hour.
Earth alkali metal soluble salt in the Preparation of Catalyst is the nitrate salt or the acetate of earth alkali metal.
Earth alkali metal soluble salt strength of solution in the Preparation of Catalyst is 0.1-2mol/L.
Sodium hydroxide in the Preparation of Catalyst, Pottasium Hydroxide or yellow soda ash, wet chemical concentration are 0.1-4mol/L.
Calcination atmosphere in the Preparation of Catalyst is air (carrying out in the retort furnace), flowing nitrogen (99.99% high-purity N
2, 30ml/min) or find time (～10
-2Pa) condition.
The present invention adopts above-mentioned catalyzer and 1, and 2-Ucar 35 material and catalyzer contact reacts, temperature of reaction are 350-700 ℃, and the best is 400-650 ℃; Reaction pressure is normal pressure-5MPa; 1, the liquid air speed 0.5～10h of 2-Ucar 35
-1, the best is 1-5h
-1Wherein, 1, the per pass conversion of 2-Ucar 35 can reach more than 60%, and the hydroxyacetone selectivity can reach more than the 90wt% in the product liquid.
Embodiment
It is a kind of 1 that the present invention provides, and 2-Ucar 35 material and solid catalyst contact reacts prepare the method for hydroxyacetone.
Through embodiment the present invention is made detailed description below, but the present invention is not limited to these embodiment.
Embodiment 1 (Preparation of Catalyst)
The preparation process of catalyst A is following: under the room temperature, be the Mg (NO of 1.5mol/L with concentration
3)
2K with 1.5mol/L
2CO
3The solution equal-volume mixes, reaction, ageing 6 hours, and after the filtration, solid drying makes magnesium basic carbonate; Magnesium basic carbonate is placed retort furnace, and 550 ℃ of roastings 4 hours obtain the MgO catalyzer.N
2It is 58m that physics adsorption desorption method records its BET specific surface area
2/ g.
Embodiment 2 (Preparation of Catalyst)
The preparation process of catalyst B is following: under 60 ℃, be the Mg (NO of 1.5mol/L with concentration
3)
2K with 1.5mol/L
2CO
3The solution equal-volume mixes, reaction, ageing 6 hours, and after the filtration, solid drying makes magnesium basic carbonate; Magnesium basic carbonate is placed retort furnace, and 550 ℃ of roastings 4 hours obtain the MgO catalyzer.N
2It is 110m that physics adsorption desorption method records its BET specific surface area
2/ g.
Embodiment 3 (Preparation of Catalyst)
The preparation process of catalyzer C is following: under 100 ℃, be the Mg (NO of 1.5mol/L with concentration
3)
2K with 1.5mol/L
2CO
3The solution equal-volume mixes, reaction, ageing 6 hours, and after the filtration, solid drying makes magnesium basic carbonate; Magnesium basic carbonate is placed retort furnace, and 550 ℃ of roastings 4 hours obtain the MgO catalyzer.N
2It is 150m that physics adsorption desorption method records its BET specific surface area
2/ g.
Embodiment 4 (Preparation of Catalyst)
The preparation process of catalyzer D is following: under the room temperature, with the Mg (NO of 1mol/L
3)
2Mix, react with the KOH solution equal-volume of 2mol/L, ageing 6 hours, after the filtration, solid drying makes Mg (OH)
2With Mg (OH)
2In finding time (～10
-2Pa) under the condition, 600 ℃ of calcinings 4 hours, make the MgO catalyzer.N
2It is 130m that physics adsorption desorption method records its BET specific surface area
2/ g.
Embodiment 5 (Preparation of Catalyst)
The preparation process of catalyzer E is following: under the room temperature, with the Ca (NO of 1mol/L
3)
2K with 1mol/L
2CO
3The solution equal-volume mixes, reaction, ageing 6 hours, and after the filtration, solid drying makes CaCO
3With CaCO
3In flowing nitrogen atmosphere, 900 ℃ of roastings 4 hours make the CaO catalyzer.N
2It is 12.3m that physics adsorption desorption method records its BET specific surface area
2/ g.
Embodiment 6 (reaction evaluating)
Use catalyst A, B, C, D, the E of embodiment 1,2,3,4,5 preparations respectively, adopt fixed-bed reactor, 1, the catalytic dehydrogenation of 2-Ucar 35 prepares hydroxyacetone.Reaction conditions is following: loaded catalyst is 1g, 400 ℃ of temperature of reaction, and raw material is 1, the 2-Ucar 35,1,2-Ucar 35 feed weight air speed is 2h
-1, reaction pressure is a normal pressure.Reaction feed was got product analysis after 1 hour, and reaction result is as shown in table 1.
The result shows; On above-mentioned catalyzer; 1, the transformation efficiency of 2-Ucar 35 is respectively 42.69%, 47.98%, 50.80%, 49.91% and 31.26%, and the selectivity of hydroxyacetone is respectively 96.12wt%, 94.76wt%, 95.36wt%, 95.82wt% and 92.17wt% in the product.
Table 1
| Catalyzer | A | B | C | D | E |
| 1,2-Ucar 35 transformation efficiency (%) | 42.69 | 47.98 | 50.80 | 49.91 | 31.26 |
| Hydroxyacetone selectivity (wt%) | 96.12 | 94.76 | 95.36 | 95.82 | 92.17 |
| Other product (wt%) | 3.88 | 5.24 | 4.64 | 4.18 | 7.83 |
*Other product comprises propylene oxide, propionic aldehyde, acetone, vinylcarbinol etc.
Embodiment 7 (reaction evaluating)
Use catalyst A, B, C, D, the E of embodiment 1,2,3,4,5 preparations respectively, adopt fixed-bed reactor, 1, the catalytic dehydrogenation of 2-Ucar 35 prepares hydroxyacetone.Reaction conditions is following: loaded catalyst is 1g, 500 ℃ of temperature of reaction, and raw material is 1, the 2-Ucar 35,1,2-Ucar 35 feed weight air speed is 2h
-1, reaction pressure is a normal pressure.Reaction feed was got product analysis after 1 hour, and reaction result is as shown in table 2.
The result shows; On above-mentioned catalyzer; 1, the transformation efficiency of 2-Ucar 35 is respectively 60.53%, 63.17%, 67.22%, 67.09% and 46.83%, and the selectivity of hydroxyacetone is respectively 90.34wt%, 91.59wt%, 91.03wt%, 91.32wt% and 87.61wt% in the product.
Table 2
| Catalyzer | A | B | C | D | E |
| 1,2-Ucar 35 transformation efficiency (%) | 60.53 | 63.17 | 67.22 | 67.09 | 46.83 |
| Hydroxyacetone selectivity (wt%) | 90.34 | 91.59 | 91.03 | 91.32 | 87.61 |
| Other product (wt%) | 9.66 | 8.41 | 8.97 | 8.68 | 12.39 |
*Other product comprises propylene oxide, propionic aldehyde, acetone, vinylcarbinol etc.
Claims (4)
1. one kind prepares the method for hydroxyacetone by the 2-Ucar 35, is catalyzer with the alkaline earth metal oxide, and 1; 2-Ucar 35 and catalyzer contact reacts, its temperature of reaction are 350-700 ℃, and reaction pressure is normal pressure-5MPa; 1, the liquid weight air speed of 2-Ucar 35 is 0.5～10h
-1, with 1, the catalytic dehydrogenation of 2-Ucar 35 generates hydroxyacetone.
2. the earth alkali metal in the method for claim 1, wherein described alkaline earth metal oxide catalyzer is one or more the mixture in magnesium, calcium, strontium and the barium.
3. according to claim 1 or claim 2 method, wherein, the earth alkali metal in the described alkaline earth metal oxide catalyzer is one or both the mixture in magnesium, the calcium.
4. the method for claim 1, wherein temperature of reaction is 400-650 ℃; Reaction pressure is normal pressure-5MPa, 1, and the liquid weight air speed of 2-Ucar 35 is 1-5h
-1
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100769501A CN101774898B (en) | 2009-01-14 | 2009-01-14 | Preparation method of acetone alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100769501A CN101774898B (en) | 2009-01-14 | 2009-01-14 | Preparation method of acetone alcohol |
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|---|---|
| CN101774898A CN101774898A (en) | 2010-07-14 |
| CN101774898B true CN101774898B (en) | 2012-08-08 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304921A (en) * | 1999-11-19 | 2001-07-25 | 西巴特殊化学品控股有限公司 | Method of using easy removed nitroxyl selective alcohol axide |
| JP2004339118A (en) * | 2003-05-14 | 2004-12-02 | Koei Chem Co Ltd | Method for producing monohydroxyacetone |
| JP2005211881A (en) * | 2004-02-02 | 2005-08-11 | Chisso Corp | Catalyst for producing hydroxy ketone and production method for hydroxy ketone using the same |
| CN101016234A (en) * | 2007-01-18 | 2007-08-15 | 复旦大学 | Method of coproducing alpha-acetol and pyruvaldehyde by 1,2-dihydroxypropane |
-
2009
- 2009-01-14 CN CN2009100769501A patent/CN101774898B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304921A (en) * | 1999-11-19 | 2001-07-25 | 西巴特殊化学品控股有限公司 | Method of using easy removed nitroxyl selective alcohol axide |
| JP2004339118A (en) * | 2003-05-14 | 2004-12-02 | Koei Chem Co Ltd | Method for producing monohydroxyacetone |
| JP2005211881A (en) * | 2004-02-02 | 2005-08-11 | Chisso Corp | Catalyst for producing hydroxy ketone and production method for hydroxy ketone using the same |
| CN101016234A (en) * | 2007-01-18 | 2007-08-15 | 复旦大学 | Method of coproducing alpha-acetol and pyruvaldehyde by 1,2-dihydroxypropane |
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