CN101362676A - Method for preparing 1,2-propylene glycol by catalytic hydrogenation of biodiesel base crude glycerine - Google Patents
Method for preparing 1,2-propylene glycol by catalytic hydrogenation of biodiesel base crude glycerine Download PDFInfo
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Abstract
The invention relates to a method for directly preparing 1,2-propylene glycol by biological diesel based crude glycerin. The biological diesel based crude glycerin is used as the raw material, and under the action of solid alkali-copper metal catalyst, the reaction is proceeded for 6-20 hours under the temperature of 180-260 DEG C, and the 1,2-propylene glycol is prepared by a batch type one-step reaction. The highest conversion rate of glycerin can reach 91.3 percent, and the yield of 1,2-propylene glycol can reach 85 percent. Compared with the existing method for preparing 1,2-propylene glycol, in the invention, the solid alkali-copper metal catalyst can effectively overcome the influence of alkaline impurity in biological diesel based crude glycerin solution. The method of the invention has the advantages of simple process, high yield, low cost, less environmental pollution and simple separation.
Description
Technical field:
What the present invention relates to is the directly preparation 1 of a kind of biodiesel base crude glycerine shortening, and the method for 2-propylene glycol particularly relates to preparation 1, copper-solid base catalyst in the method for 2-propylene glycol and preparation method.
Background technology:
1, (1,2-Propylene glycol is called for short 1 to the 2-propylene glycol, 2-PDO), is a kind of colourless, thickness, stable water-absorbent liquid, and almost tasteless odorless is inflammable.Fusing point-60 ℃.187.3 ℃ of boiling points, relative density 1.036 (25/4 ℃) is with water, ethanol and multiple immiscible organic solvent.In easily oxidation more than 150 ℃.1, the 2-propylene glycol is the important source material of unsaturated polyester, Resins, epoxy, urethane resin, and this unsaturated polyester is used for topcoating and reinforced plastics in a large number.1, the viscosity of 2-propylene glycol and good hygroscopicity, and nontoxic, thereby in food, medicine and cosmetic industry, be widely used as moisture adsorbent, antifreezing agent, lubricant and solvent.In foodstuffs industry, propylene glycol and fatty acid response generate propylene glycol fatty acid ester, mainly as food emulsifier; Propylene glycol is the fine solvent of seasonings and pigment.1, the 2-propylene glycol is commonly used for solvent, tenderizer and the vehicle etc. of making all kinds of ointment, ointment in medicine industry, because propylene glycol has mutual solubility preferably with all kinds of spices, thereby also is used as the solvent of makeup and tenderizer or the like.Propylene glycol is also as tobacco moistening agent, mould inhibitor, the solvent of food processing plant lubricating oil and food labeling printing ink.The aqueous solution of propylene glycol is effective antifreezing agent.
Present 1, the production method of 2-propylene glycol mainly contains three kinds: (1) propylene oxide direct hydration method is a pressurization non-catalytic hydrolyzing method; Under 150-160 ℃, 0.78-0.98MPa pressure, direct hydration makes by propylene oxide and water, and reaction product is through evaporation, rectifying, finished product.(2) the indirect hydration method of propylene oxide is done the indirect hydration of catalyzer by propylene oxide and water with sulfuric acid and is made.(3) the direct catalytic oxidation of propylene.These methods exist problems such as the serious and cost costliness of environmental pollution, are difficult to scale operation.Simultaneously, because the quick rise of petrochemical material prices such as propylene, the cost of above-mentioned production technique is also more and more higher, so the direct shortening preparation 1 of research and development low cost, efficient, eco-friendly heterogeneous catalysis glycerine, and the method for 2-propylene glycol has great importance.
From glycerine preparation 1, the 2-propylene glycol has had some patent reports, as: German patent DE-PS-541362 has reported glycerine hydrogenation preparation 1 under the nickel-base catalyst effect the earliest, the method of 2-propylene glycol, but reaction needed just can be carried out at (more than 270 degree) under the very high temperature, have a large amount of gaseous products to generate (mainly being methane) simultaneously in the reaction, thereby wastage of material yield serious, the purpose product is not high.European patent EP-A-72629 has described the polyvalent alcohol hydrogenation process (centre also comprises glycerine) under a kind of nickel, platinum, the palladium catalyst effect, in order to obtain corresponding dibasic alcohol, must add mineral alkali in reaction solution.This technology is also adopted by afterwards a lot of research papers (Journal of Catalysis 249 (2007) 328-337 and Catalysis Letters 117 (2007) 62-67), but pollutes big, product separation difficulty.U.S. Pat 4642394 has been described under the homogeneous catalyst effect of tungstenic and group VIII element, and glycerine and synthesis gas reaction prepare the method for propylene glycol, when adopting methyl ethyl diketone rhodium carbonyl and H
2WO
4Acid is solvent, temperature of reaction 200 degree, synthetic gas (CO:H for catalyzer, 1-Methyl-2-Pyrrolidone
2=1:2) pressure 4600psig, the reaction times 24 hours, propylene glycol yield 44%, n-propyl alcohol yield 4%; The product yield of this patent is low, reaction pressure is high, and homogeneous catalyst is difficult to Separation and Recovery and metal rhodium catalyzer and costs an arm and a leg etc. and to make it less economical, does not have competitive power.U.S. Pat 5214219 has been reported a kind of glycerine production 1 that is used for, and the method for 2-propylene glycol, this method are utilized the bimetal loaded catalyst of Cu and Zn.But temperature of reaction is higher than 250 ℃, hydrogen pressure more than 150 normal atmosphere, and catalyst consumption higher (be the 5-15% of glycerine), glycerol concentration low (20-40%) are difficult to the realization industrialization simultaneously.It is the glycerine hydrogenation preparation 1 that catalyzer carries out that U.S. Pat 5276181 provides a kind of Ru/ activated carbon with sulfide and alkali modification, the method of 2-propylene glycol, under the condition of the massfraction 30% of temperature 240 degree, hydrogen pressure 130 normal atmosphere, glycerine, the selectivity of propylene glycol is still very low.U.S. Pat 5616817 and Chinese patent CN1061968C have reported glycerine hydrogenation preparation 1 on the Co-Cu-Mn-Mo catalyzer, the method of 2-propylene glycol, but reaction pressure high especially (250 normal atmosphere), and Preparation of catalysts method complexity, facility investment height, 1, the selectivity of 2-propylene glycol is very low.Chinese invention patent application CN200610105255.X discloses a kind of by glycerine hydrogenation preparation 1, and the method for 2-propylene glycol reaction, this method adopt the CuO-SiO of pure hot method preparation
2Catalyzer, be reflected at the severe toxicity methanol solvate in carry out.Chinese invention patent application CN101085719 discloses the directly hydrogenizing glycerol preparation 1 under the effect of a kind of polycomponent compound Co-Cu-Al series catalysts, the technology of 2-propylene glycol, but react that needed temperature is above at 220 degree, reaction pressure more than 100 normal atmosphere, catalyst consumption big (catalyst levels accounts for and reacts more than 2% of feed liquid) simultaneously.
In recent years, along with the fast development of biofuel industry, glycerine will increase year by year as the output of the main by product in the production of biodiesel process; According to estimates, will be to the output of biodiesel base crude glycerine in 2010 above 1,200,000 tons, superfluous 500,000 tons.Therefore, the propylene glycol that with the biodiesel base crude glycerine is the raw material production high added value is the important outlet that solves the superfluous problem of glycerine, and the sound development that promotes biofuel and biomass energy industry is had great importance.
Though above-mentioned serial patent of invention all reported set out by glycerine synthetic 1, the technology of 2-propylene glycol, ubiquitous problem is: temperature of reaction height (generally 220 spend more than), reaction pressure height (generally more than 100 normal atmosphere); Do not take into full account the concrete characteristics of biodiesel base crude glycerine simultaneously, that is: in biodiesel base crude glycerine, the content of glycerine is roughly 80-85%, in the raw material except water, contain the catalyzer of a spot of production biofuel (as alkali (NaOH, Ca (OH) toward contact
2And NaH
2PO
4Deng), residual production of biodiesel raw material and component (as: methyl alcohol, glycerine alkyl acid methyl esters), relate in addition in the disclosed in front patent of this part impurity; Wherein mineral alkali has toxic action to the solid acid catalyst that the overwhelming majority has dehydration activity.
Summary of the invention
The objective of the invention is at containing a small amount of alkaline impurities, residual biodiesel fuel component in the biodiesel base crude glycerine, and the temperature of reaction height, the propylene glycol productive rate is low, cost is high and problem such as environmental pollution, it is raw material, direct hydrogenation preparing 1 that a kind of biodiesel base crude glycerine that can directly adopt is provided, the technology of 2-propylene glycol and catalyzer.
Preparation 1 provided by the invention, the method of 2-propylene glycol, be that directly to adopt biodiesel base crude glycerine be raw material, under the effect of the copper catalyst of basic supports load, intermittent type single step reaction preparation 1, the method of 2-propylene glycol, have that technology is simple, temperature of reaction is low, productive rate is high, cost is low, low in the pollution of the environment, separate simple advantage.
Solution of the present invention is: adopt the alkali solid material to eliminate and break away from the influence of a small amount of alkaline impurities in the biodiesel base crude glycerine, with the copper of solid alkali material load as catalyzer, a step is realized the glycerine hydrogenation preparation 1 in the solution in different concentration, 2-propylene glycol in autoclave.
Biodiesel base crude glycerine shortening provided by the invention directly prepares 1, the method of 2-propylene glycol, with the biodiesel base crude glycerine without purification is raw material, reductive agent is a high-purity hydrogen, under the effect of the copper catalyst of solid alkali material load, catalytic hydrogenolysis biodiesel base crude glycerine, intermittent type single step reaction preparation 1, the 2-propylene glycol, preparation process is as follows:
1). with qualities of glycerin concentration is the biodiesel base crude glycerine solution of 15%-90%, join in the stainless steel autoclave that has liner, add the copper catalyst of solid alkali material load then in biodiesel base crude glycerine solution, the quality of the copper in the control catalyst is that the ratio of qualities of glycerin is 1/100-1/10000;
2). with after the aforesaid reaction vessel sealing, fall air in the reactor with hydrogen exchange, charge into the hydrogen of certain pressure then, the initial hydrogen atmospheric pressure is lower than 30 normal atmosphere;
3). heat temperature raising, make the temperature in the reactor reach 180-260 ℃, start agitator simultaneously, reacted 6-20 hour;
4). after reaction finished, with the reactor cool to room temperature, first centrifugation, decompress filter again made reaction product solution and catalyst separating, catalyst recovery.
The copper catalyst of solid alkali material load of the present invention mainly comprises: adopt the metallic copper of magnesium oxide, hydrotalcite, aluminium sesquioxide, Beta molecular sieve, HZSM5 molecular sieve, silicon-dioxide even load, the charge capacity of copper is 5-30wt%.The copper catalyst of solid alkali material load adopts incipient impregnation, coprecipitation method and the preparation of precipitation sedimentation.
The copper catalyst of solid alkali material load of the present invention, as follows with the step of equi-volume impregnating preparation:
(1) with magnesium oxide, hydrotalcite, aluminium sesquioxide, Beta molecular sieve, HZSM5 molecular sieve, silica supports 400-550 ℃ of following pre-treatment 4 hours;
(2) take by weighing the pretreated carrier of certain mass, be impregnated into certain density CuCl
2In the aqueous solution, carry out incipient impregnation, the charge capacity of control metallic copper is 5-30wt%;
(3) the above-mentioned catalyzer for preparing was at room temperature left standstill 12 hours, in 110 ℃ of baking ovens dry 12 hours then, last roasting 4 hours in 550 ℃ air atmosphere.
The copper catalyst of magnesium oxide load of the present invention, as follows with the step of coprecipitation method preparation:
(1) takes by weighing the MgCl of certain mass respectively
26H
2O and CuCl
22H
2O under agitation mixes both, and copper and magnesian mass ratio are 0.05-0.3:1 in the control solution, and the concentration of metal ion is in the 0.1-3.0 mol in the control aqueous solution;
(2) under condition of stirring, the sodium carbonate solution of 1.0 mol is added drop-wise to MgCl
26H
2O and CuCl
22H
2In the mixed aqueous solution of O, after the pH value of solution reaches 10, stop to drip sodium carbonate solution, continue to stir 30min;
(3) will leave standstill under the aforesaid liquid room temperature 12 hours, carry out decompress filter then; With the distilled water wash precipitation, repeat 4 times;
What (4) will obtain was deposited in 110 ℃ of baking ovens dry 12 hours, roasting 4 hours in muffle furnace in 550 ℃ air atmosphere then.
Magnesium oxide loaded metal copper catalyst of the present invention, as follows with the step of precipitation sedimentation preparation:
(1) takes by weighing a certain amount of magnesium hydroxide suspension in the aqueous solution, at room temperature with the CuCl for preparing
22H
2O solution and sodium carbonate solution also flow, are added drop-wise under condition of stirring in the magnesian suspension, and the charge capacity of control metallic copper is 5-30wt%, the pH value 5-10 of solution;
(2) dropwise after, continue to stir 30min, left standstill then 12 hours;
(3) carry out decompress filter,, repeat 4 times with the distilled water wash precipitation;
What (4) will obtain is deposited in 110 ℃ of baking ovens dry 12 hours;
(5) roasting 4 hours in muffle furnace in 550 ℃ air atmosphere.
Above-mentioned catalyzer reductase 12 hour in the hydrogen stream of certain temperature before the reaction.
Advantage of the present invention:
Biodiesel base crude glycerine shortening of the present invention directly prepares 1, and the method for 2-propylene glycol is being raw material without the biodiesel base crude glycerine of purifying, contain in this raw material a spot of production of biodiesel catalyzer (as alkali: NaOH, Ca (OH)
2, NaH
2PO
4), residual biodiesel fuel component (as: methyl alcohol, glycerine alkyl acid methyl esters, C14-C18 alkyl acid sodium etc.), relate in addition in the disclosed in front patent of this part impurity, as representative, representational raw glycerine is composed as follows in the embodiments of the invention: glycerine: 85.1% (weight percent, as follows), C14-C17 alkanoic acid methyl esters 8.3%, methyl alcohol: 3.3%, water: 2.8%, C14-C17 alkanoic acid sodium: 0.4%, NaOH+Ca (OH)
2Deng: 0.1%.
The influence of a small amount of alkaline impurities in the biodiesel base crude glycerine can be eliminated and break away to copper-solid base catalyst of the present invention, and this catalyzer not only has very high activity, and low to the purity requirement of raw material.Catalyst levels is few, and the mass ratio of glycerine/metal is greater than 100 in the reaction system.
Reaction conditions gentleness of the present invention, reaction pressure low (the initial hydrogen atmospheric pressure is lower than 30 normal atmosphere), temperature of reaction are lower than 230 degree.Under the effect of Cu/MgO catalyzer, the transformation efficiency of glycerine is up to 91.3%, 1, and the molar yield of 2-propylene glycol reaches 85%.
Embodiment:
Embodiment 1
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 5wt% to add 0.5 gram Cu/MgO catalyzer, immersion process for preparing), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 20 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 72.5% and 1, and the molar yield of 2-propylene glycol is 67%.
Embodiment 2
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 5wt% to add 0.5 gram Cu/MgO catalyzer, immersion process for preparing), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 12 hours.After reaction finishes, the reactor cool to room temperature, first centrifugation, decompress filter reaction solution again make reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 61% and 1, and the molar yield of 2-propylene glycol is 57.5%.
Embodiment 3
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 5wt% to add 0.5 gram Cu/MgO catalyzer, immersion process for preparing), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 44.7% and 1, and the molar yield of 2-propylene glycol is 42%.
Embodiment 4
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 10wt% to add 0.5 gram Cu/MgO catalyzer, immersion process for preparing), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 56% and 1, and the molar yield of 2-propylene glycol is 49%.
Embodiment 5
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 15wt% to add 0.5 gram Cu/MgO catalyzer, immersion process for preparing), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 51% and 1, and the molar yield of 2-propylene glycol is 43.6%.
Embodiment 6
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 20wt% to add 0.5 gram Cu/MgO catalyzer, immersion process for preparing), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 42.6% and 1, and the molar yield of 2-propylene glycol is 39%.
Embodiment 7
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 10wt% to add 0.5 gram Cu/MgO catalyzer, the coprecipitation method preparation), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 74.7% and 1, and the molar yield of 2-propylene glycol is 65%.
Embodiment 8
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 15wt% to add 0.5 gram Cu/MgO catalyzer, the coprecipitation method preparation), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 74% and 1, and the molar yield of 2-propylene glycol is 65%.
Embodiment 9
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 10wt% to add 0.5 gram Cu/MgO catalyzer, the preparation of precipitation sedimentation), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 69% and 1, and the molar yield of 2-propylene glycol is 63%.
Embodiment 10
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams, adding distilled water is 30wt% with the concentration dilution of glycerine, (the Cu charge capacity is 10wt% to add 0.5 gram Cu/MgO catalyzer, the coprecipitation method preparation), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 77.5% and 1, and the molar yield of 2-propylene glycol is 70.6%.
Embodiment 11
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams, adding distilled water is 45wt% with the concentration dilution of glycerine, (the Cu charge capacity is 10wt% to add 0.5 gram Cu/MgO catalyzer, the coprecipitation method preparation), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 86.7% and 1, and the molar yield of 2-propylene glycol is 80%.
Embodiment 12
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams, adding distilled water is 60wt% with the concentration dilution of glycerine, (the Cu charge capacity is 10wt% to add 0.5 gram Cu/MgO catalyzer, the coprecipitation method preparation), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 91.3% and 1, and the molar yield of 2-propylene glycol is 85%.
Embodiment 13
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams, adding distilled water is 75wt% with the concentration dilution of glycerine, (the Cu charge capacity is 10wt% to add 0.5 gram Cu/MgO catalyzer, the coprecipitation method preparation), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 88.5% and 1, and the molar yield of 2-propylene glycol is 82.7%.
Embodiment 14
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, (the Cu charge capacity is 10wt% to add 0.5 gram Cu/MgO catalyzer, the coprecipitation method preparation), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 180 ℃, reacts 6 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 41% and 1, and the molar yield of 2-propylene glycol is 38.5%.
Embodiment 15
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams and put in the autoclave, add Cu/ hydrotalcite catalyst (the Cu charge capacity is 5wt%), the sealing back charges into the hydrogen of 3.0MPa then with the air in the hydrogen exchange reactor.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 20 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 4% and 1, and the molar yield of 2-propylene glycol is 3.8%.
Embodiment 16
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, add 0.5 gram Cu/ aluminum trioxide catalyst (the Cu charge capacity is 5wt%), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 20 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 3.7% and 1, and the molar yield of 2-propylene glycol is 2%.
Embodiment 17
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams joins in the autoclave, add 0.5 gram Cu/Beta molecular sieve catalyst (the Cu charge capacity is 5wt%), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 20 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 4.1% and 1, and the molar yield of 2-propylene glycol is 3.8%.
Embodiment 18
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, add 0.5 gram Cu/ZSM5 molecular sieve catalyst (the Cu charge capacity is 5wt%), with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 20 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 6% and 1, and the molar yield of 2-propylene glycol is 5%.
Embodiment 19
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams and put in the autoclave, add 0.5 gram Cu/SiO
2Catalyzer (the Cu charge capacity is 5wt%) with the air in the hydrogen exchange reactor, charges into the hydrogen of 3.0MPa after the sealing then.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 20 hours.After reaction finishes, the reactor cool to room temperature, the decompress filter reaction solution makes reaction product solution and catalyst separating, and analyzing the transformation efficiency that obtains glycerine is 3% and 1, and the molar yield of 2-propylene glycol is 2%.
Claims (5)
1, a kind of biodiesel base crude glycerine shortening directly prepares 1, and the method for 2-propylene glycol is characterized in that: be raw material with the biodiesel base crude glycerine, under the effect of the copper catalyst of solid alkali material load, intermittent type single step reaction preparation 1, the 2-propylene glycol, preparation process is as follows:
(1). with qualities of glycerin concentration is the biodiesel base crude glycerine solution of 15%-90%, join in the stainless steel autoclave that has liner, add copper-solid base catalyst then in biodiesel base crude glycerine solution, the quality of the copper in the control catalyst is that the ratio of qualities of glycerin is 1/100-1/10000;
(2). with after the aforesaid reaction vessel sealing, fall air in the reactor with hydrogen exchange, charge into the hydrogen of certain pressure then, the initial hydrogen atmospheric pressure is lower than 30 normal atmosphere;
(3). heat temperature raising, make the temperature in the reactor reach 180-260 ℃, start agitator simultaneously, reacted 6-20 hour;
(4). after reaction finished, with the reactor cool to room temperature, first centrifugation, decompress filter again made reaction product solution and catalyst separating, catalyst recovery.
2, according to the described preparation 1 of claim 1, the method of 2-propylene glycol, it is characterized in that: the copper catalyst of the solid alkali material load that is adopted comprises: adopt magnesium oxide, hydrotalcite, aluminium sesquioxide, Beta molecular sieve, HZSM5 molecular sieve, silicon dioxide carried metallic copper, the charge capacity of copper metal is 5-30wt%.
3, glycerine according to claim 1 and 2 is through direct hydrogenation preparing 1, and the method for 2-propylene glycol is characterized in that the copper catalyst of solid alkali material load adopting the preparation process of equi-volume impregnating preparation as follows:
(1) with magnesium oxide, hydrotalcite, aluminium sesquioxide, Beta molecular sieve, HZSM5 molecular sieve, silica supports 400-550 ℃ of following pre-treatment 4 hours;
(2) take by weighing the pretreated carrier of certain mass, be impregnated into certain density CuCl
2In the aqueous solution, carry out incipient impregnation, the charge capacity of control metallic copper is 5-30wt%;
(3) at room temperature, left standstill 12 hours, in 110 ℃ of baking ovens dry 12 hours then, last roasting 4 hours in 550 ℃ air atmosphere obtained copper-solid base catalyst with the above-mentioned catalyzer for preparing.
4, glycerine according to claim 1 and 2 is through direct hydrogenation preparing 1, and the method for 2-propylene glycol is characterized in that: the solid alkali material that is adopted is a magnesium oxide, and the copper catalyst of described magnesium oxide load adopts the preparation process of coprecipitation method preparation as follows:
(1) takes by weighing the MgCl of certain mass respectively
26H
2O and CuCl
22H
2O under agitation mixes both, and copper and magnesian mass ratio are 0.05-0.3:1 in the control solution, and the concentration of metal ion is in the 0.1-3.0 mol in the control aqueous solution;
(2) under condition of stirring, the sodium carbonate solution of 1.0 mol is added drop-wise to MgCl
26H
2O and CuCl
22H
2In the mixed aqueous solution of O, after the pH value of solution reaches 10, stop to drip sodium carbonate solution, continue to stir 30min;
(3) at room temperature, left standstill 12 hours, carry out decompress filter then aforesaid liquid; With the distilled water wash precipitation, repeat 4 times;
What (4) will obtain was deposited in 110 ℃ of baking ovens dry 12 hours, and in 550 ℃ air atmosphere, roasting is 4 hours in the muffle furnace then.
5, according to claim 1 or the direct hydrogenation preparing 1 of 2 described glycerine warps, the method for 2-propylene glycol is characterized in that: the solid alkali material that is adopted is a magnesium oxide, and the copper catalyst of described magnesium oxide load adopts the preparation process of precipitation sedimentation preparation as follows:
(1) takes by weighing a certain amount of magnesium hydroxide suspension in the aqueous solution, at room temperature with the CuCl for preparing
22H
2O solution and sodium carbonate solution also flow, are added drop-wise under condition of stirring in the magnesian suspension, and the charge capacity of control metallic copper is 5-30wt%, the pH value 5-10 of solution;
(2) dropwise after, continue to stir 30min, left standstill then 12 hours;
(3) carry out decompress filter,, repeat 4 times with the distilled water wash precipitation;
What (4) will obtain is deposited in 110 ℃ of baking ovens dry 12 hours;
(5) roasting 4 hours in muffle furnace in 550 ℃ air atmosphere.
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| CN102166525A (en) * | 2011-03-16 | 2011-08-31 | 浙江大学 | Copper-rhodium-magnesium-aluminum four-component catalyst for preparing 1,2-propylene glycol by adding hydrogen directly to biodiesel-based crude glycerine and preparation method of 1,2-propylene glycol |
| US8022257B2 (en) | 2009-09-03 | 2011-09-20 | The Ohio State University Research Foundation | Methods for producing polyols using crude glycerin |
| CN102198402A (en) * | 2011-03-16 | 2011-09-28 | 浙江大学 | Cu-Pd-Mg-Al four-component catalyst for preparing 1,2-propylene glycol (1,2-PDO) by hydrogenation of biodiesel-based crude glycerin as well as preparation method thereof |
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| CN104058933A (en) * | 2014-06-23 | 2014-09-24 | 上海康沃生化科技有限公司 | Biodiesel based crude glycerol catalytic hydrogenolysis method for preparation of propylene glycol |
| CN104549347A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparation of 1, 2-propylene glycol through glycerol hydrogenation as well as preparation method and application of catalyst |
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| CN100560552C (en) * | 2006-12-07 | 2009-11-18 | 中国科学院兰州化学物理研究所 | Glycerine hydrogenation preparation 1, the method for 2-propylene glycol |
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| CN104058933A (en) * | 2014-06-23 | 2014-09-24 | 上海康沃生化科技有限公司 | Biodiesel based crude glycerol catalytic hydrogenolysis method for preparation of propylene glycol |
| CN116354908A (en) * | 2023-05-25 | 2023-06-30 | 山东联欣环保科技有限公司 | Preparation method and application of all-bio-based propylene oxide |
| CN116354908B (en) * | 2023-05-25 | 2023-09-19 | 山东联欣环保科技有限公司 | Preparation method and application of all-bio-based propylene oxide |
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