CN102633599A - Hydrogenation method of 1,2-propylene glycol by bio-based glycerol - Google Patents
Hydrogenation method of 1,2-propylene glycol by bio-based glycerol Download PDFInfo
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- CN102633599A CN102633599A CN2012101162945A CN201210116294A CN102633599A CN 102633599 A CN102633599 A CN 102633599A CN 2012101162945 A CN2012101162945 A CN 2012101162945A CN 201210116294 A CN201210116294 A CN 201210116294A CN 102633599 A CN102633599 A CN 102633599A
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Abstract
The invention discloses a hydrogenation method of 1,2-propylene glycol by bio-based glycerol. The method comprises the following steps: filling a catalyst in a continuous fixed bed reactor, pressurizing a glycerol solution and hydrogen to flow into the reactor, and controlling the reaction temperature to be between 180 and 240 DEG C and the reaction pressure to be between 1.2 and 2.5MPa, wherein the solvent in the glycerol is methanol or ethanol, and the ratio of Cu, Zn, Al and V in the catalyst is (20-50):(10-50):(10-50):(1-5). The 1,2-propylene glycol hydrogenated by the bio-based glycerol has the advantages of low temperature, low pressure and mild reaction condition; and the stability of the catalyst is high.
Description
Technical field
The present invention is specifically related to a kind of biological base glycerol hydrogenation and synthesizes 1, the method for 2-Ucar 35.
Background technology
Because the fast development of biofuel, diesel oil by-product per ton went out 10% glycerine in recent years, because the output of a large amount of glycerine but do not have the development of derived product, drug on the market in market to making glycerine, and price declines to a great extent.1, the 2-Ucar 35 can be used as the raw material of unsaturated polyester, in a large number as frostproofer, also is the raw material of softening agent, tensio-active agent, emulsifying agent and emulsion splitter.Can be used as mould inhibitor, fruit ripener, sanitas, frostproofer and tobacco wetting Agent for Printing Inks.Prior art during the 2-Ucar 35, adopt HTHP, and catalyst stability is low utilizing glycerine hydrogenation preparation 1 more.
Summary of the invention
To the objective of the invention is the defective that exists in the prior art in order solving, to provide the gentle hydrogenation of a kind of low-temp low-pressure, reaction conditions synthetic 1, the method for 2-Ucar 35.
In order to achieve the above object; The invention provides a kind of biological base glycerol hydrogenation synthetic 1; The method of 2-Ucar 35 may further comprise the steps: loading catalyzer in the fixed-bed reactor continuously, with glycerine solution and hydrogen inflow reactor; Control reaction temperature 180-240 ℃, reaction pressure 1.2-2.5MPa; Solvent in the glycerine solution is selected from methyl alcohol or ethanol; Catalyzer contains Cu, Zn, Al and V, and mass ratio is 20-50:10-50:10-50:1-5, and preferred mass is than being 40-50:20-30:20-40:1-3.
Wherein, the concentration of glycerine solution is 20-80%, and mass space velocity is 0.2-0.5/h, and hydrogen-oil ratio is 600-1500.
Catalyzer is the co-precipitated catalyst of Cu-Zn-V-Al, and the mass ratio of Cu, Zn, V and Al is 20-50:10-50:1-5:10-50, and preferred mass is than being 40-50:20-30:1-3:20-40, and its preparation method is following:
(1) ageing: get cupric nitrate, zinc nitrate, aluminum nitrate and metavanadate and be prepared into the aqueous solution (preferred concentration is 1mol/L), add sodium carbonate solution (preferred concentration is 1mol/L), regulate pH value to 8, heavyization 4 hours filtered;
(2) washing: it is constant to be precipitated to washings pH value with distilled water wash;
(3) pre-prepared: with 110 ℃ of dryings of washed throw out in the step (2) 6 hours, 350 ℃ of roastings 5 hours formed the catalyzer that Cu-Zn-V-Al forms.
Compression molding is with progressively heating reduction activation to 300 ℃ of hydrogen before use for this catalyzer, and the reduction activation time is 24 hours.
The present invention compares prior art and has the following advantages: the employing active ingredient is that copper, cocatalyst component are that zinc and vanadium, carrier are the co-precipitated catalyst of aluminum oxide, and activity stabilized, the transformation efficiency of product and selectivity all are higher than 90%; While low temperature reaction low pressure, mild condition; And raw material adopts technical grade glycerine still can reach higher transformation efficiency and selectivity, compares pharmaceutical grade glycerine and has practiced thrift cost.
Embodiment
Below in conjunction with specific embodiment biological base glycerol hydrogenation of the present invention is synthesized 1, the method for 2-Ucar 35 is elaborated.
Embodiment one
Preparation of Catalyst: is 45/27/25/3 to be mixed with the aqueous solution that total concn is 1mol/L with the nitrate salt of Cu, Zn, Al and sodium metavanadate according to the Cu/Zn/Al/V mass ratio, stirs down to the Na that wherein drips 1mol/L
2CO
3Solution, regulating pH value is about 8 back ageings 4 hours, filtration, washing precipitation is 7,110 ℃ of dry 6h to washings pH, 350 ℃ of roastings 5 hours.
Compression molding was with progressively heating reduction activation to 300 ℃ of hydrogen, total 24 hours recovery times before the above-mentioned catalyzer that obtains used.
Hydrogenation is synthetic: getting solvent is that methyl alcohol, concentration are 40% glycerine solution, in the 100ml fixed bed hydrogenation reactor, carries out hydrogenation and synthesizes, underlying condition: air speed 0.5/h, hydrogen-oil ratio 600, pressure 2MPa, temperature 220 degree.
Reaction back glycerol conversion yield is 97%, reaction make 1,2-Ucar 35 selectivity is 92%.
Embodiment two
Preparation of Catalyst: is 40/30/29/1 to be mixed with the aqueous solution that total concn is 1mol/L with the nitrate salt of Cu, Zn, Al and ammonium meta-vanadate according to the Cu/Zn/Al/V mass ratio, stirs down to the Na that wherein drips 1mol/L
2CO
3Solution, regulating pH value is about 8 back ageings 4 hours, filtration, washing precipitation is 7,110 ℃ of dry 6h to washings pH, 350 ℃ of roastings 5 hours.
Compression molding was with hydrogen heating reduction activation to 300 ℃ 24 hours total recovery times progressively before the above-mentioned catalyzer that obtains used.
Hydrogenation is synthetic: the technical grade glycerine of getting the pharmaceutical grade 95% that biodiesel byproduct produces; It with ethanol is 60% glycerine solution for the solvent compound concentration; It is synthetic in the 100ml fixed bed hydrogenation reactor, to carry out hydrogenation, principal reaction condition: air speed 1.0/h, hydrogen-oil ratio 1000; Pressure 2.5MPa, 220 ℃ of temperature.
Reaction back glycerol conversion yield is 95%, reaction make 1,2-Ucar 35 selectivity is 90%.
Embodiment three
Catalyzer and reaction conditions are with embodiment two, and the glycerine that hydrogenation uses reaction raw materials to choose is the 95% technical grade glycerine of producing from biodiesel byproduct.
Reaction back glycerol conversion yield is 95%, reaction make 1,2-Ucar 35 selectivity is 90%.
Embodiment four
Preparation of Catalyst: is 25/25/46/4 to be mixed with the aqueous solution that total concn is 1mol/L with the nitrate salt of Cu, Zn, Al and sodium metavanadate according to the Cu/Zn/Al/V mass ratio, stirs down to the Na that wherein drips 1mol/L
2CO
3Solution, regulating the pH value is about 8 back ageings 4 hours, filters, washing precipitation is 7,110 ℃ of dry 6h to washings pH, 350 degree roastings 5 hours.
Compression molding was with hydrogen heating reduction activation to 300 ℃ 24 hours total recovery times progressively before the above-mentioned catalyzer that obtains used.
Hydrogenation is synthetic: getting the glycerine of the technical grade 99.5% that biodiesel byproduct produces, with ethanol is 20% glycerine solution for the solvent compound concentration, and it is synthetic in the 100ml fixed bed hydrogenation reactor, to carry out hydrogenation; Principal reaction condition: air speed 1.0; Hydrogen-oil ratio 1000, pressure 2.5MPa, 220 ℃ of temperature.
Reaction back glycerol conversion yield is 95%, reaction make 1,2-Ucar 35 selectivity is 90%.
Claims (8)
1. a biological base glycerol hydrogenation synthesizes 1, and the method for 2-Ucar 35 is characterized in that; May further comprise the steps: loading catalyzer in the fixed-bed reactor continuously; With glycerine solution and hydrogen inflow reactor, control reaction temperature 180-240 ℃, reaction pressure 1.2-2.5MPa; Solvent in the said glycerine solution is selected from methyl alcohol or ethanol; Said catalyzer contains Cu, Zn, Al and V, and mass ratio is 20-50:10-50:10-50:1-5.
2. biological base glycerol hydrogenation according to claim 1 synthesizes 1, and the method for 2-Ucar 35 is characterized in that: the mass ratio of Cu, Zn, V and Al is 40-50:20-30:1-3:20-40 in the said catalyzer.
3. biological base glycerol hydrogenation according to claim 1 synthesizes 1, and the method for 2-Ucar 35 is characterized in that: the concentration of glycerine solution is 20-80%.
4. biological base glycerol hydrogenation according to claim 1 synthesizes 1, and the method for 2-Ucar 35 is characterized in that: the mass space velocity of said glycerine solution is 0.2-1.0/h.
5. biological base glycerol hydrogenation according to claim 1 synthesizes 1, and the method for 2-Ucar 35 is characterized in that: the volume ratio of said hydrogen and glycerine solution is 600-1500:1.
6. biological base glycerol hydrogenation according to claim 1 synthesizes 1, and the method for 2-Ucar 35 is characterized in that: said catalyzer is the co-precipitated catalyst of Cu-Zn-V-Al, and the mass ratio of said Cu, Zn, V and Al is 20-50:10-50:1-5:10-50.
7. biological base glycerol hydrogenation according to claim 6 synthesizes 1, and the method for 2-Ucar 35 is characterized in that: the preparation method of said co-precipitated catalyst comprises:
(1) ageing: get cupric nitrate, zinc nitrate, aluminum nitrate and metavanadate and be prepared into the aqueous solution, add sodium carbonate solution, regulate pH value to 8, ageing 4 hours is filtered;
(2) washing: it is constant to be precipitated to washings pH value with distilled water wash;
(3) pre-prepared: with 110 ℃ of dryings of washed throw out in the step (2) 6 hours, 350 ℃ of roastings 5 hours formed the catalyzer that Cu-Zn-V-Al forms.
8. biological base glycerol hydrogenation according to claim 7 is synthetic 1, and the method for 2-Ucar 35 is characterized in that: said co-precipitated catalyst before use, with hydrogen heating reduction activation to 300 degree progressively; The said reduction activation time is 24 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101162945A CN102633599A (en) | 2012-04-20 | 2012-04-20 | Hydrogenation method of 1,2-propylene glycol by bio-based glycerol |
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| CN2012101162945A CN102633599A (en) | 2012-04-20 | 2012-04-20 | Hydrogenation method of 1,2-propylene glycol by bio-based glycerol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942449A (en) * | 2012-11-23 | 2013-02-27 | 上海药明康德新药开发有限公司 | Synthetic method of 2,2-bis (trifluoroethyl) propanol |
| CN103864574A (en) * | 2012-12-12 | 2014-06-18 | 山东经典化工股份有限公司 | Production technology of 1,2-propylene glycol |
| CN107628929A (en) * | 2017-09-26 | 2018-01-26 | 南京工业大学 | Production process for preparing 1, 2-propylene glycol by glycerol hydrogenolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012149A (en) * | 2007-02-07 | 2007-08-08 | 南京工业大学 | Method for continuously preparing 1, 2-propylene glycol by catalytic hydrogenation of glycerol |
| CN101054339A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
| WO2010150278A2 (en) * | 2009-06-15 | 2010-12-29 | Ganapati Dadasaheb Yadav; | Hydrogenolysis of polyhydroxy alcohols using metal incorporated manganese oxide octahedral molecular sieve as a catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101012149A (en) * | 2007-02-07 | 2007-08-08 | 南京工业大学 | Method for continuously preparing 1, 2-propylene glycol by catalytic hydrogenation of glycerol |
| CN101054339A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
| WO2010150278A2 (en) * | 2009-06-15 | 2010-12-29 | Ganapati Dadasaheb Yadav; | Hydrogenolysis of polyhydroxy alcohols using metal incorporated manganese oxide octahedral molecular sieve as a catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942449A (en) * | 2012-11-23 | 2013-02-27 | 上海药明康德新药开发有限公司 | Synthetic method of 2,2-bis (trifluoroethyl) propanol |
| CN102942449B (en) * | 2012-11-23 | 2015-01-07 | 无锡药明康德生物技术有限公司 | Synthetic method of 2,2-bis (trifluoroethyl) propanol |
| CN103864574A (en) * | 2012-12-12 | 2014-06-18 | 山东经典化工股份有限公司 | Production technology of 1,2-propylene glycol |
| CN107628929A (en) * | 2017-09-26 | 2018-01-26 | 南京工业大学 | Production process for preparing 1, 2-propylene glycol by glycerol hydrogenolysis |
| CN107628929B (en) * | 2017-09-26 | 2020-09-25 | 南京工业大学 | Production process for preparing 1, 2-propylene glycol by glycerol hydrogenolysis |
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Application publication date: 20120815 |