CN100497274C - Method for preparing 1,3 propylene glycol by using glycerol method - Google Patents
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- CN100497274C CN100497274C CNB2007100194577A CN200710019457A CN100497274C CN 100497274 C CN100497274 C CN 100497274C CN B2007100194577 A CNB2007100194577 A CN B2007100194577A CN 200710019457 A CN200710019457 A CN 200710019457A CN 100497274 C CN100497274 C CN 100497274C
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Abstract
This invention discloses a method for preparing 1, 3-propylene glycol from glycerol. The method has such advantages as high catalytic activity, mild reaction conditions, high product selectivity, high product purity, simple process. The method comprises: (1) adding 95% glycerol and 30% oxydol into a round bottom flask, setting condensing tube and drying tube, heating to 100 deg.C under stirring, and reacting for 1-3 h to obtain acetone alcohol; (2) adding acetone alcohol into a pressure reaction kettle loaded with transition oxometalate catalyst, introducing hydrogen for 4-6 h at 100-200 deg.C and 10 MPa, reacting, and rectifying to obtain 1,3-propylene glycol.
Description
Technical field
The present invention relates to a kind of preparation 1,3-propylene glycol, be equipped with the method for 1,3-propylene glycol more specifically to a kind of glycerine legal system.
Background technology
Glycerine is the important source material of military project, light industry, chemical industry, in recent years along with grease chemical article expanding production continuously of biofuel particularly, seriously drug on the market to cause its by-product glycerin, price significantly glides, be that the exploitation that raw material carries out derived product is the method that well solves the glycerine surplus with glycerine, if can develop the production method of suitable derived product, can reduce the production cost of derived product again.(it is a kind of important chemical material that 1,3-propanediol is called for short 1,3-PD) to 1,3-propylene glycol, and its most important purposes is exactly as one of monomer of synthesizing new polyester (as PTT).PTT is a monomer synthetic polyester than with other glycol, and (PET) has better performance as polyethylene terephthalate, has therefore obtained paying close attention to widely.1,3-PD can also improve the performance of product as the component in the product, as the fuel of makeup, antifreezing agent printer ink, sanitising agent, stablizer and fuel cell etc.1,3-PD is used for industries such as food, makeup and pharmacy as the intermediate of medicine and organic synthesis in addition.
1,3-PD has the number of chemical synthetic method.At present realized that the chemical synthesis process of suitability for industrialized production mainly is acrolein hydration method and oxirane carbonyl method, also have other research unit to develop such as formaldehyde acetaldehyde condensation preparation 1,3-PD, ethene are through Prins reaction synthetic 1,3-PD, with glycerine the chemical synthesis process of raw material through chemical reaction preparation 1,3-PD etc.The acrolein hydration method is to be the industrialized route of raw material production 1,3-PD with the propenal, and its shortcoming is that propenal itself also is a kind of important organic intermediate, and belongs to hypertoxic combustible and explosive articles, is difficult to store and transportation.The oxirane carbonyl method is to make raw material with oxyethane (being called for short EO); obtain 3-hydroxy propanal through hydroformylation reaction; hydrogenation obtains 1,3-PD then, the shortcoming plant investment height of this technology; while effective catalyst system complexity; manufacture craft is harsh and unstable, the selection of ligand supertoxic agent and improvement, and reaction pressure is higher in addition; hydroformylation reaction pressure is about 10MPa, and structure of reactor is quite complicated.Formaldehyde acetaldehyde condensation preparation 1,3-PD is the process that formaldehyde and acetaldehyde is condensed into 3-HPA by catalyzer KOH, after spent ion exchange resin removes KOH, with aluminum isopropylate its reduction is made 1 again, 3-PD, this method has the advantage that raw material is easy to get, but the aluminum isopropylate consumption is big, the cost of producing 1,3-PD is than higher.Excessive along with the grease chemical article by-product glycerin, the glycerine legal system is equipped with 1, ammediol promptly is feedstock production 1 with glycerine, ammediol then becomes ideal preparation 1, the method of ammediol, the glycerine legal system is equipped with 1 at present, what ammediol generally adopted at present is biological enzyme, but the activity and the life-span of biological enzyme production cost costliness, enzyme are limited, to the ingredient requirement harshness, and for the activity that guarantees enzyme is also high to the requirement of reaction environment, so need the new preparation 1 of exploitation glycerine method, the method for ammediol.
Summary of the invention
The objective of the invention is to solve deficiency and the problem that exists in the above-mentioned present technology, provide a kind of glycerine legal system to be equipped with the method for 1,3-propylene glycol.
Technical scheme of the present invention is as follows:
A kind of glycerine legal system is equipped with the method for 1,3-propylene glycol, may further comprise the steps:
A) glycerine of 95% purity, the hydrogen peroxide of 30% concentration are joined respectively in the round-bottomed flask, install prolong and drying tube, be warming up to 100 ℃ of reactions 1～3 hour under stirring, stopped reaction obtains hydroxyacetone;
B) again the hydroxyacetone that obtains is joined in the autoclave of putting the oxo transition metal phosphate catalyst in advance well, under 10MPa pressure, 100～120 ℃ of conditions of temperature, feed hydrogen 4～6 hours continuously, behind the stopped reaction, pass through rectifying separation, obtain 1, ammediol.
Above-mentioned glycerine legal system is equipped with the method for 1,3-propylene glycol, its steps A) described in the consumption of hydrogen peroxide be glycerine weight; The consumption of the oxo transition metal phosphate catalyst step B) is 1～5% of a hydroxyacetone weight.
Above-mentioned a kind of glycerine legal system is equipped with 1, used oxo transition metal phosphate catalyst in the method for 3-propylene glycol, the empirical formula of this oxo transition metal phosphate catalyst is: PaWbXcOd, wherein, P is the element of a kind of Fe of being selected from and Cr at least, W is a kind of element that is selected from following element at least: Mo, V, W, Ti, Zr, X is a kind of element that is selected from following element at least: Ni, Co, Cu, Mn, Zn, La, Nd, Y, and a=1, b=0.01-1.0, c=0.01-1.0, d depend on the oxidation state of other element.
Above-mentioned a kind of glycerine legal system is equipped with the preparation method of oxo transition metal phosphate catalyst used in the method for 1,3-propylene glycol, and its step is as follows:
1) dissolving
The metal-salt of P, W, X is comprised that metal oxide, metal chloride, metal acetate, metal sulfate and metal nitrate all are dissolved in the polar solvent in the ratio among the PaWbXcOd, form saturated metal salt solution, described P is the element of a kind of Fe of being selected from and Cr at least, W is a kind of element that is selected from following element at least: Mo, V, W, Ti, Zr, X is a kind of element that is selected from following element at least: Ni, Co, Cu, Mn, Zn, La, Nd, Y, and a=1, b=0.01-1.0, c=0.01-1.0, d depend on the oxidation state of other element; Described polar solvent is water or alcohol; Described alcohol is preferably methyl alcohol, ethanol, propyl alcohol, ethylene glycol or propylene glycol.
2) precipitation
After saturated metal salt solution preparation is finished, add the precipitation agent alkaline hydrated oxide and form colloidal precipitation; Described oxyhydroxide is sodium hydroxide, potassium hydroxide or ammoniacal liquor, and the concentration of alkaline hydrated oxide is at 0.01～10mol/L, and the concentration of alkaline hydrated oxide is preferably 0.1～1mol/L; The consumption of alkaline hydrated oxide will make saturated metal salt solution become colloidal precipitation, and promptly 90～100% saturated metal salt solution is retained in the colloidal precipitation;
3) aging
Colloidal sol just wears out once forming, and promptly leaves standstill 1 hour to 3 weeks obtaining gel; Preferred 4 hours to 100 hours, more preferably 6 hours to 60 hours.
4) washing
To weakly alkaline, promptly the pH value is 8～9 with the gel thorough washing, and used washing composition is deionization ammoniumsulphate soln, ammonium chloride solution or ammonium nitrate solution during washing, and the concentration of washing composition is generally at 0.1～10mol/L; Washing composition is preferably ammonium nitrate solution, and concentration is preferably 0.5～2mol/L.
5) drying
Gel is carried out drying remove solvent, obtain the exsiccant gel; Described drying means preferably includes vacuum-drying, lyophilize, spraying drying, rotary evaporator or dry air; Described vacuum-drying is carried out under the pressure range of 10～550mmHg, described lyophilize in nitrogen or argon gas, temperature in is that 125 ℃～200 ℃ and temperature out are to carry out under 75 ℃～150 ℃, described rotary evaporator is to carry out under 25 ℃～90 ℃ temperature, the 10～760mmHg pressure range bathing temperature, and described dry air is to carry out in 25 ℃-90 ℃ temperature range;
6) calcining
The exsiccant gel was calcined 0.5～30 hour under 350 ℃～850 ℃ conditions, obtained the oxo transition metal phosphate catalyst.
The temperature that calcining is carried out is generally 350 ℃～850 ℃, and preferred 400 ℃～700 ℃, more preferably 500 ℃～640 ℃.The time that calcining is carried out will be suitable for forming above-mentioned catalyzer.Usually, in order to obtain needed improved oxometallic acid salt catalyst, calcining was carried out 0.5～30 hour, preferred 1～25 hour, more preferably carried out 1～15 hour.In preferred operator scheme, calcining was undertaken by two stages.In the fs, sintering is 15 minutes～8 hours in the oxidative environment (for example air) of catalyzer under 200 ℃～400 ℃ preferred 275 ℃～325 ℃ temperature, preferred 1～3 hour.In subordinate phase, sintering is 15 minutes～48 hours in the non-oxidizable environment (for example rare gas element) of the material that will make the fs under 500 ℃～750 ℃ preferred 550 ℃～650 ℃, and preferred 1～24 hour, most preferably 2～10 hours.Described rare gas element is nitrogen, argon gas, xenon, helium or their mixture.Preferred rare gas element is xenon or nitrogen.
In particularly preferred Implementation Modes, will the incinerating material place in the needed oxidizing atmosphere at room temperature, be elevated to the fs calcining temperature then, and needed calcination time of lasting fs.Replacing former atmosphere with the needed non-oxidizing atmosphere of second calcination stage then is elevated to subordinate phase with temperature and calcines needed temperature and continue subordinate phase and calcine the needed time.
The invention has the beneficial effects as follows:
1, catalytic activity height, the reaction conditions gentleness; 2, target product selectivity is good, and product purity height, per pass conversion can reach more than 95%, and product purity can reach 97%; 3, catalyzer easily separates with product, and technology is simple; 4, catalyzer is reusable, also can use continuously; 5, little to conversion unit corrodibility; 6 production costs are low, and economic benefit is good, so glycerine production 1,3-propylene glycol route has the bigger market competitiveness.
Embodiment
Embodiment 1
The 100ml aqueous solution (preparing being dissolved in the water under 70 ℃ of the corresponding salt) that will contain chromium nitrate hydrate (1.0M Cr), potassium wolframate (0.5M W) and venus crystals (0.25M Cu) joins in the 500ml flask.The aqueous solution with sodium hydroxide (0.5M) is a shape adding wherein then.In 15-30 minute, form the reddish-brown gel.With ammonium nitrate solution (1mol/L) repetitive scrubbing gelatinous mass to pH=8-9.By remove with rotary evaporator anhydrate after, with further dry a whole night, calcining then in 25 ℃ vacuum drying oven of solid matter.(calcining is performed such, and solid matter is placed in the air atmosphere, is heated to 275 ℃ and kept 1 hour with the speed of 10 ℃/min in 275 ℃ air atmosphere then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 2 hours with the speed of 2 ℃/min from 275 ℃ 600 ℃ of argon gas.) nominal of final catalyzer consists of Cr
1W
0.5Cu
0.25O
x
The hydrogen peroxide of glycerine, 30 milliliter of 30% concentration of 10 grams, 95% purity join respectively in 200 milliliters the round-bottomed flask, install prolong and drying tube, stir and are warming up to 100 ℃ of reactions 2 hours down, and stopped reaction obtains 9.0 and restrains hydroxyacetones.Join put well in advance 0.25 restrain in 500 milliliters of autoclaves of catalyzer, under 10MPa pressure, 110 ℃ of conditions of temperature, fed hydrogen 5 hours continuously, stopped reaction.By rectifying separation, obtain 7.8 grams 1, ammediol, its purity 96%.
Embodiment 2
The 100ml aqueous solution (preparing being dissolved in the water under 70 ℃ of the corresponding salt) that will contain chromium nitrate hydrate (1.0M Cr), potassium wolframate (0.5M W) and venus crystals (0.25M Cu) joins in the 500ml flask.The aqueous solution with sodium hydroxide (0.5M) is a shape adding wherein then.In 15-30 minute, form the reddish-brown gel.Left standstill 72 hours in shady place under 20 ℃.With ammonium nitrate solution (1mol/L) repetitive scrubbing gelatinous mass to pH=8-9.By remove with rotary evaporator anhydrate after, with solid matter further dry a whole night in 25 ℃ vacuum drying oven, reclaim and obtain the 34g solid catalyst precursor.Then with this solid catalyst precursor calcining of 17g.Calcining is performed such, and solid matter is placed in the air atmosphere, is heated to 275 ℃ and keep 1 hour with the speed of 10 ℃/min in 275 ℃ air atmosphere then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 2 hours with the speed of 2 ℃/min from 275 ℃ 600 ℃ of argon gas.The nominal of final catalyzer consists of Cr
1W
0.5Cu
0.25O
x
The hydrogen peroxide of glycerine, 30 milliliter of 30% concentration of 10 grams, 95% purity join respectively in 200 milliliters the round-bottomed flask, install prolong and drying tube, stir and are warming up to 100 ℃ of reactions 2 hours down, and stopped reaction obtains 9.0 and restrains hydroxyacetones.Join put well in advance 0.5 restrain in 500 milliliters of autoclaves of catalyzer, under 10MPa pressure, 100 ℃ of conditions of temperature, fed hydrogen 6 hours continuously, stopped reaction.By rectifying separation, obtain 7.9 grams 1, ammediol, its purity 97%.
Embodiment 3
To calcine in the following manner by the other 17g solid catalyst precursor of embodiment 2 preparation: solid matter is placed in the air atmosphere, is heated to 275 ℃ and in 275 ℃ air atmosphere, kept 1 hour with the speed of 10 ℃/min then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 5 hours with the speed of 2 ℃/min from 275 ℃ 600 ℃ of argon gas.The nominal of final catalyzer consists of Cr
1W
0.5Cu
0.25O
x
The hydrogen peroxide of glycerine, 30 milliliter of 30% concentration of 10 grams, 95% purity join respectively in 200 milliliters the round-bottomed flask, install prolong and drying tube, stir and are warming up to 100 ℃ of reactions 2 hours down, and stopped reaction obtains 9.0 and restrains hydroxyacetones.Join put well in advance 0.25 restrain in 500 milliliters of autoclaves of catalyzer, under 10MPa pressure, 120 ℃ of conditions of temperature, fed hydrogen 4 hours continuously, stopped reaction.By rectifying separation, obtain 8.0 grams 1, ammediol, its purity 96.5%.
Embodiment 4
The 100ml aqueous solution (preparing being dissolved in the water under 70 ℃ of the corresponding salt) that will contain chromium nitrate hydrate (1.0M Cr), potassium wolframate (0.5M W) and venus crystals (0.25M Cu) joins in the 500ml flask.Then sodium hydroxide (0.5M) solution is and drips the shape adding wherein.In 15-30 minute, form the reddish-brown gel.Left standstill 72 hours in shady place under 20 ℃.With ammonium nitrate solution (1mol/L) repetitive scrubbing gelatinous mass to pH=8-9.By remove with rotary evaporator anhydrate after, with solid matter further dry a whole night in 25 ℃ vacuum drying oven, reclaim and obtain the 34g solid catalyst precursor.Then with this solid catalyst precursor calcining of 17g.Calcining is performed such, and solid matter is placed in the air atmosphere, is heated to 275 ℃ and keep 10 hours with the speed of 10 ℃/min in 275 ℃ air atmosphere then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 2 hours with the speed of 2 ℃/min from 275 ℃ 600 ℃ of argon gas.The nominal of final catalyzer consists of Cr
1W
0.5Cu
0.25O
x
The hydrogen peroxide of glycerine, 30 milliliter of 30% concentration of 10 grams, 95% purity join respectively in 200 milliliters the round-bottomed flask, install prolong and drying tube, stir and are warming up to 100 ℃ of reactions 2 hours down, and stopped reaction obtains 9.0 and restrains hydroxyacetones.Join real the making in 500 milliliters of autoclaves of catalyzer of 0.20 gram of putting well in advance, under 10MPa pressure, 110 ℃ of conditions of temperature, fed hydrogen 5 hours continuously, stopped reaction.By rectifying separation, obtain 8.0 grams 1, ammediol, its purity 97%.
Embodiment 5
To calcine in the following manner by the other 17g solid catalyst precursor of embodiment 4 preparation: solid matter is placed in the air atmosphere, is heated to 275 ℃ and in 275 ℃ air atmosphere, kept 1 hour with the speed of 10 ℃/min then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 15 hours with the speed of 2 ℃/min from 275 ℃ 600 ℃ of argon gas.The nominal of final catalyzer consists of Cr
1W
0.5Cu
0.25O
x
The hydrogen peroxide of glycerine, 30 milliliter of 30% concentration of 10 grams, 95% purity join respectively in 200 milliliters the round-bottomed flask, install prolong and drying tube, stir and are warming up to 100 ℃ of reactions 2 hours down, and stopped reaction obtains 9.0 and restrains hydroxyacetones.Join put well in advance 0.25 restrain in 500 milliliters of autoclaves of catalyzer, under 10MPa pressure, 110 ℃ of conditions of temperature, fed hydrogen 5 hours continuously, stopped reaction.By rectifying separation, obtain 8.0 grams 1, ammediol, its purity 97%.
Embodiment 6
The 100ml aqueous solution (preparing being dissolved in the water under 70 ℃ of the corresponding salt) that will contain chromium nitrate hydrate (1.0M Cr), potassium wolframate (0.5M W) and venus crystals (0.25M Cu) joins in the 500ml flask.Then the 35wt% ammonia soln is and drips the shape adding wherein.In 15-30 minute, form the reddish-brown gel.Left standstill 72 hours in shady place under 20 ℃.With ammonium nitrate solution (1mol/L) repetitive scrubbing gelatinous mass to pH=8-9.By remove with rotary evaporator anhydrate after, with solid matter further dry a whole night in 25 ℃ vacuum drying oven, reclaim and obtain the 34g solid catalyst precursor.Then with this solid catalyst precursor calcining of 17g.Calcining is performed such, and solid matter is placed in the air atmosphere, is heated to 275 ℃ and keep 10 hours with the speed of 10 ℃/min in 275 ℃ air atmosphere then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 2 hours with the speed of 2 ℃/min from 275 ℃ 600 ℃ of argon gas.The nominal of final catalyzer consists of Cr
1W
0.5Cu
0.25O
x
The hydrogen peroxide of glycerine, 30 milliliter of 30% concentration of 10 grams, 95% purity join respectively in 200 milliliters the round-bottomed flask, install prolong and drying tube, stir and are warming up to 100 ℃ of reactions 2 hours down, and stopped reaction obtains 9.0 and restrains hydroxyacetones.Join put well in advance 0.25 restrain in 500 milliliters of autoclaves of catalyzer, under 10MPa pressure, 110 ℃ of conditions of temperature, fed hydrogen 5 hours continuously, stopped reaction.By rectifying separation, obtain 7.6 grams 1, ammediol, its purity 96.5%.
Claims (8)
1, a kind of glycerine legal system is equipped with the method for 1,3-propylene glycol, may further comprise the steps:
A) glycerine of 95% purity, the hydrogen peroxide of 30% concentration are joined respectively in the round-bottomed flask, install prolong and drying tube, be warming up to 100 ℃ of reactions 1～3 hour under stirring, stopped reaction obtains hydroxyacetone;
B) again the hydroxyacetone that obtains is joined in the autoclave of putting the oxo transition metal phosphate catalyst in advance well, under 10MPa pressure, 100～120 ℃ of conditions of temperature, feed hydrogen 4～6 hours continuously, behind the stopped reaction, pass through rectifying separation, obtain 1, ammediol; The empirical formula of wherein said oxo transition metal phosphate catalyst is: PaWbXcOd, and wherein P is the Cr element, and W is the W element, and X is the Cu element, and a=1, b=0.01-1.0, c=0.01-1.0, d depend on the oxidation state of other element.
2, glycerine legal system according to claim 1 is equipped with the method for 1,3-propylene glycol, it is characterized in that steps A) described in the consumption of hydrogen peroxide be 2～3 times of glycerine weight; The consumption of the oxo transition metal phosphate catalyst step B) is 1～5% of a hydroxyacetone weight.
3, a kind of glycerine legal system according to claim 1 is equipped with the preparation method of oxo transition metal phosphate catalyst used in the method for 1,3-propylene glycol, it is characterized in that step is as follows:
1) dissolving
With the metal-salt of P, W, X is that metal chloride, metal acetate, metal sulfate or metal nitrate all are dissolved in the polar solvent in the ratio among the PaWbXcOd, form saturated metal salt solution, described P is the Cr element, W is the W element, X is the Cu element, and a=1, b=0.01-1.0, c=0.01-1.0, d depend on the oxidation state of other element; Described polar solvent is water or alcohol;
2) precipitation
After saturated metal salt solution preparation is finished, add the precipitation agent alkaline hydrated oxide and form colloidal precipitation; Described oxyhydroxide is sodium hydroxide, potassium hydroxide or ammoniacal liquor, the concentration of alkaline hydrated oxide is at 0.01～10mol/L, the consumption of alkaline hydrated oxide will make saturated metal salt solution become colloidal precipitation, and promptly 90～100% saturated metal salt solution is retained in the colloidal precipitation;
3) aging
Colloidal sol just wears out once forming, and promptly leaves standstill 1 hour to 3 weeks obtaining gel;
4) washing
To weakly alkaline, promptly the pH value is 8～9 with the gel thorough washing, and used washing composition is deionization ammoniumsulphate soln, ammonium chloride solution or ammonium nitrate solution during washing, and the concentration of washing composition is at 0.1～10mol/L;
5) drying
Gel is carried out drying remove solvent, obtain the exsiccant gel;
6) calcining
The exsiccant gel was calcined 0.5～30 hour under 350 ℃～850 ℃ conditions, obtained the oxo transition metal phosphate catalyst.
4, the preparation method of oxo transition metal phosphate catalyst according to claim 3 is characterized in that the alcohol described in the step 1) dissolving is methyl alcohol, ethanol, propyl alcohol, ethylene glycol or propylene glycol; Step 2) concentration of the alkaline hydrated oxide described in the precipitation is 0.1～1mol/L; Time of repose described in step 3) is aging is 4 hours to 100 hours; Washing composition described in the step 4) washing is an ammonium nitrate solution, and concentration is 0.5～2mol/L; Drying means described in the step 5) drying is vacuum-drying, lyophilize, spraying drying, rotary evaporator or dry air; Calcining temperature described in the step 6) calcining is 400 ℃-700 ℃, and calcination time is 1～25 hour.
5, the preparation method of oxo transition metal phosphate catalyst according to claim 4 is characterized in that the time of repose of step 3) described in aging is 6 hours to 60 hours; The dry described vacuum-drying of step 5) is carried out under the pressure range of 10～550mmHg, described lyophilize in nitrogen or argon gas, temperature in is that 125 ℃～200 ℃ and temperature out are to carry out under 75 ℃～150 ℃, described rotary evaporator is to carry out under 25 ℃～90 ℃ temperature, the 10～760mmHg pressure range bathing temperature, and described dry air is to carry out in 25 ℃-90 ℃ temperature range; Calcining temperature described in the step 6) calcining is 500 ℃～640 ℃, and calcination time is 1～15 hour.
6, ask the preparation method of 3 described oxo transition metal phosphate catalysts according to right, it is characterized in that the calcining described in the step 6) calcining undertaken by two stages, fs, sintering is 15 minutes～8 hours in the air of catalyzer under 200 ℃～400 ℃ temperature; Subordinate phase, sintering is 15 minutes～48 hours in the rare gas element of the material that will make the fs under 500 ℃～750 ℃, and described rare gas element is nitrogen, argon gas, xenon, helium or their mixture.
7, ask the preparation method of 6 described oxo transition metal phosphate catalysts according to right, it is characterized in that the fs described in the step 6) calcining is a sintering 1～3 hour in the air of catalyzer under 275 ℃～325 ℃ temperature; Subordinate phase is sintering in the rare gas element of material under 550 ℃～650 ℃ that will make the fs 1～24 hour, and described rare gas element is nitrogen or xenon.
8, ask the preparation method of 7 described oxo transition metal phosphate catalysts according to right, it is characterized in that step 6) calcines described subordinate phase and be sintering in the rare gas element of material under 550 ℃～650 ℃ that will make the fs 2～10 hours.
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| CN101456791B (en) * | 2007-12-13 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Method for producing 1,2-propanediol by using biological base glycerol |
| US8101807B2 (en) * | 2008-12-23 | 2012-01-24 | Uop Llc | Methods for converting glycerol to propanol |
| US20110207972A1 (en) * | 2010-02-23 | 2011-08-25 | Battelle Memorial Institute | Catalysts and processes for the hydrogenolysis of glycerol and other organic compounds for producing polyols and propylene glycol |
| CN106824191B (en) * | 2015-12-04 | 2019-05-14 | 中国科学院大连化学物理研究所 | Bimetallic catalyst prepares the application in 1,3- propylene glycol in hydrogenolysis of glycerin |
| PL3400208T3 (en) * | 2016-01-07 | 2021-12-27 | Haldor Topsøe A/S | Process for the preparation of ethylene glycol from sugars |
| CN106220472B (en) * | 2016-08-02 | 2018-06-12 | 黄山市徽州天马化工有限公司 | A kind of method of glycerin chlorination production dichlorohydrin |
| CN109400611B (en) * | 2018-09-27 | 2021-08-24 | 南京林业大学 | Synthesis method of 1-vinyl-4, 5-dihydropyrrole [1,2-a ] quinoxaline compound |
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