CN102188982A - Copper-ruthenium-magnesium-aluminum tetra ingredient catalyst used to prepare 1, 2-propylene glycol through directly adding hydrogen into biodiesel based crude glycerine - Google Patents
Copper-ruthenium-magnesium-aluminum tetra ingredient catalyst used to prepare 1, 2-propylene glycol through directly adding hydrogen into biodiesel based crude glycerine Download PDFInfo
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- CN102188982A CN102188982A CN2011100629880A CN201110062988A CN102188982A CN 102188982 A CN102188982 A CN 102188982A CN 2011100629880 A CN2011100629880 A CN 2011100629880A CN 201110062988 A CN201110062988 A CN 201110062988A CN 102188982 A CN102188982 A CN 102188982A
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Abstract
The invention discloses a copper-ruthenium-magnesium-aluminum tetra ingredient catalyst used to prepare 1, 2-propylene glycol prepared through directly adding hydrogen into biodiesel based crude glycerine and a preparation method of the catalyst. A copper-ruthenium-magnesium-aluminum tetra ingredient catalyst is synthesized in one step with a coprecipitation method. After roasting and reduction, the catalyst can be directly used to prepare 1, 2-propylene glycol through directly adding hydrogen into biodiesel based crude glycerine. A high efficiency synthesis of 1, 2-propylene glycol can be realized in a mild and green condition. The highest yield rate of 1, 2-propylene glycol can achieve 67.8 percent when 75 percent of glycerin aqueous solution is directly added into hydrogen at a temperature of 180 DEG C and a hydrogen pressure of 2.0 MPa and the reaction lasts for 10 hours.
Description
Technical field
The present invention relates to the direct hydrogenation preparing 1 of a kind of biodiesel base crude glycerine, the Catalysts and its preparation method of 2-propane diols.More particularly, be the direct hydrogenation preparing 1 of a kind of biodiesel base crude glycerine, the copper-ruthenium of 2-propane diols-magnesium-aluminium four component catalysts and preparation method thereof.
Background technology
1, (1,2-Propylene glycol is called for short 1 to the 2-propane diols, 2-PDO), is a kind of colourless, thickness, stable water imbibition liquid, and almost odorless, tasteless is inflammable.Fusing point-60 ℃, 187.3 ℃ of boiling points, relative density 1.036(25/4 ℃), with water, ethanol and multiple immiscible organic solvent, in easily oxidation more than 150 ℃.
1, the 2-propane diols is the important source material of unsaturated polyester (UP), epoxy resin, polyurethane resin, and this unsaturated polyester (UP) is used for surface coating and reinforced plastics in a large number.1, the viscosity of 2-propane diols and good hygroscopicity and nontoxic, thereby in food, medicine and cosmetics industry, be widely used as hygroscopic agent, antifreeze, lubricant and solvent.In food industry, 1,2-propane diols and fatty acid response generate methyl glycol fatty acid ester, mainly as food emulsifying agent; Simultaneously, 1, the 2-propane diols also is the fine solvent of flavouring and pigment.
1, the 2-propane diols is commonly used for solvent, softening agent and the excipient etc. of making all kinds of ointment, ointment in medical industry, because 1,2-propane diols and all kinds of spices have better intersolubility, thereby also is used as the solvent of cosmetics and softening agent etc.1, the 2-propane diols is also as tobacco humidizer, mould inhibitor, the solvent of food processing equipment lubricating oil and food labeling printing ink.1, the aqueous solution of 2-propane diols is effective antifreeze.
Present 1, the production method of 2-propane diols mainly contains three kinds: (1) expoxy propane direct hydration method is a pressurization non-catalytic hydrolyzing method.Under 150-160 ℃, 0.78-0.98MPa pressure, direct hydration makes by expoxy propane and water, and product is through evaporation, rectifying, finished product; (2) the indirect hydration method of expoxy propane is done the indirect hydration of catalyst by expoxy propane 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, be difficult to large-scale production, simultaneously, because the quick rise of petrochemical material prices such as propylene, the cost of above-mentioned production technology is also more and more higher, therefore the preparation of low, efficient, the eco-friendly heterogeneous catalysis glycerine of research and development cost hydrogenolysis 1, and it is particularly important that the method for 2-propane diols seems.
German patent DE-PS-541362 has reported pure glycerin hydrogenation preparing 1 under the nickel-base catalyst effect the earliest, the method of 2-propane diols, but reaction needed just can be carried out at (more than 270 degree) under the very high temperature, there is a large amount of gaseous products to generate (mainly being methane) simultaneously in the reaction, thereby wastage of material is serious, and the yield of purpose product is very low.
European patent EP-A-72629 has described the polyalcohol hydrogenation process (centre also comprises glycerine) under a kind of nickel, platinum, the palladium catalyst effect, but in order to obtain corresponding dihydroxylic alcohols, must add liquid inorganic base (NaOH or KOH) in reactant liquor.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.Meanwhile, under the condition that this liquid base exists, the carbon-carbon bond easy fracture in the glycerine generates accessory substance [Journal of Catalysis 250 (2007) 94 – 101; Science 330 (2010) 74-78].
1993, U.S. Pat 5 214 219 was reported a kind of pure glycerin production 1, reaction process of 2-propane diols of being used for.This method is utilized Cu and Zn bimetallic supported catalyst, but reaction temperature is higher than 220 ℃, Hydrogen Vapor Pressure more than 10MPa, catalyst consumption higher (being the 5-15% of concentration of substrate) simultaneously, concentration of substrate low (20-40%), the industrialization of still being unrealized so far.
A kind of Cu-Al-M that adopts organic formwork agent to induce down preparation is disclosed among the Chinese patent CN101816936
(M=Ni, Zn, Sn, Co, Fe, Mn, Ti, W) three component catalysts are used for glycerine hydrogenation under 170-220 degree, 20-50 atmospheric pressure, and the fixed bed reaction technology of continuous-flow has been adopted in reaction, and the consumption of hydrogen is higher, H
2The amount of substance of/glycerine is than between 4/1-10/1.
(A is Ti to disclose a kind of Cu-Zr-A among the Chinese patent CN200810034426.3; W; a kind of among the Mo) catalyst; this catalyst adopts the prepared by co-precipitation technology under the surfactant protection; when being used for the glycerine hydrogenation reaction; adopted trickle bed liquid-phase hydrogenatin technology, the consumption of hydrogen is higher, H
2The amount of substance of/glycerine is than between 2/1-400/1, and reaction temperature is at the 180-250 degree, reaction pressure 30-80 atmospheric pressure.
A kind of CuO-SiO is disclosed among the Chinese patent CN200610105255.X
2Catalyst, this catalyst is used for glycerine hydrogenation under 140-200 degree, 40-100 atmospheric pressure, this catalyst is better for the glycerine hydrogenation effect in the methanol solution, active high in the continuity method fixed bed reactors, but methanol solvate price height, inflammable, poisonous.
CuO-CeO is disclosed among the Chinese patent CN200710305964.7
2-SiO
2Catalyst based, the methanol solution that this catalyst can be used for continuity method fixed bed reactors, glycerine carries out hydrogenation reaction, and the consumption of the hydrogen that is adopted in the technology is very high, H
2The amount of substance ratio of/glycerine is at 1000/1-2500/1.
Disclose a kind of catalyst of 1-95%A-98-0.1%B-98-0%C form of complexity among the Chinese patent CN200710043282.8, wherein A is Cu or Zn, and B is Zn, Ga, Al, Mn or Si, and C is Al, Cr, Si, Zn or Zr.This catalyst can be used for the hydrogenation reaction of continuity method fixed bed reactors, glycerine.
Chinese patent CN200810019133.8 discloses the method that hydrogenolysis that a kind of combined oxidation copper-zine oxide-aluminium oxide catalyst is used for continuity method fixed bed reactors, glycerine prepares propane diols, the volume ratio of the hydrogen/glycerine that is adopted in the technology is 750-1200, reaction temperature 180-250 degree, reaction pressure 30-50 atmospheric pressure.
Chinese patent CN200710020031.3 discloses a kind of under 200-250 degree, 25-50 atmospheric pressure, in the continuity method fixed bed reactors, the hydrogenolysis of glycerine prepares the method for propane diols, the catalyst that patent is applied for is four component Cu-Zn-Mn-Al catalyst.
The reaction process of the biodiesel base crude glycerine hydrogenation preparing propane diols under a kind of metal-solid base bifunctional catalyst effect is disclosed among Chinese patent CN200810120727.8 and the CN200810120728.2, though adopt the batch autoclave reaction process, but the reaction time reaches 20 hours, and reaction temperature is also up to the 180-260 degree.
Chinese patent CN200810228573.4 discloses a kind of Ag and Cu jointly as the catalyst of active component preparation, but the reaction temperature among the embodiment all more than 200 degree, the productive rate of propane diols is low, the highest propane diols productive rate has only 47.5%.
Chinese patent CN200810072333.X discloses the preparation method of the improved copper-zinc catalyst of a kind of CNT and has been used for the technology of glycerine hydrogenation reaction, and after 18 hours, the conversion ratio of glycerine is at 44-in 200 degree reactions
Between 74%, the selectivity of propane diols is between 69-81%.
Chinese patent CN200880001278.3 and CN200780037555.1 disclose that a kind of to use purity be the glycerine of 95wt% at least and hydrogen under the temperature of the Hydrogen Vapor Pressure of 20-100 crust and 180-240 degree, are comprising 20-
There is reaction down in the catalyst of 60wt% cupric oxide, 30-70wt% zinc oxide and 1-10wt% manganese oxide.
Chinese patent CN200880019968.1,200880113528.2,200880113527.8 and 200880113
573.8 in a kind of glycerine hydrogenation technology of a plurality of reactor series connection is all disclosed.In addition, also have a lot of patents to adopt bio-fermentation process by glycerine preparation 1,2-propane diols.
Described in the above application for patent can be found: the reaction process majority is fixed bed reactors, the reaction temperature height, and hydrogen usage is big, and the treating capacity of glycerine is low, and also has patent to adopt poisonous methyl alcohol as solvent.Though also have and adopt the batch autoclave reactor in the application of patent, but the temperature of reaction is high or be raw material with highly purified glycerine, because the glycerine of preparation high concentration needs higher energy consumption, simultaneously, since also contain in the biodiesel base crude glycerine a certain amount of residual catalyst (mainly be NaOH, Ca (OH)
2, NaH
2PO
4Deng), subtractive process complexity, the cost of glycerine are very high, therefore directly adopt the crude glycerine hydrogenation preparation 1 that contains a certain amount of aqueous solution, 2-propane diols to have higher practical value and potential industrialization possibility.
The present invention is directed to the concrete feature that contains certain water in the biodiesel base crude glycerine, contains micro-base catalyst, invented a kind of preparation technology simple, can directly use crude glycerine hydrogenation preparing 1, the Catalysts and its preparation method of 2-propane diols, adopting this catalyst and biodiesel base crude glycerine is raw material, under gentle, green condition, realize 1, the efficient of 2-propane diols synthesized, and has significant industrial value.
Summary of the invention
The objective of the invention is to develop and a kind ofly can directly use crude glycerine hydrogenation preparing 1, the Catalysts and its preparation method of 2-propane diols, adopting this catalyst and biodiesel base crude glycerine is raw material, realizes 1 under gentle, green condition, and the efficient of 2-propane diols synthesized.
Concrete technical scheme of the present invention is as follows:
The present invention is the direct hydrogenation preparing 1 of a kind of biodiesel base crude glycerine, copper-the ruthenium of 2-propane diols-magnesium-aluminium four component catalysts and preparation method thereof, adopt synthetic copper-ruthenium of one step of coprecipitation-magnesium-aluminium four component catalysts, after roasting, reduction, can directly use and be raw material hydrogenation preparing 1 with biodiesel base crude glycerine, in the 2-propane diols, the Preparation of catalysts step is as follows:
(1), prepares the mixed solution of certain density copper nitrate, magnesium nitrate, aluminum nitrate and ruthenic chloride, Cu in the control solution
2+, Mg
2+, Al
3+Concentration be respectively 0.025,0.35,0.125mol/L, Ru
3+Concentration is 0.001mol/L;
(2), the mixed solution (alkali lye) of preparation certain density NaOH and sodium carbonate, control solution O H
-, CO
3 2-Concentration is respectively 0.8,0.25mol/L;
(3), above-mentioned metal ion solution and alkali lye are added drop-wise in the mixer according to 1/1 ratio, the temperature of control mixed liquor is that the pH value of 25 degree, mixed liquor is 9-10;
(4), above-mentioned precipitation was transferred in the flask 120 degree crystallization 20-30 hour;
(5), sediment that crystallization is good filter, spend deionised water to pH value of filtrate less than 7, be transferred to baking oven then in 80 degree dried overnight;
(6), the sample that drying is good was transferred in the Muffle furnace, in 400 degree roastings 4 hours;
(7), before above-mentioned catalyst uses, reduction is 1.5 hours in 300 degree, hydrogen stream, the flow of control hydrogen is at 40ml/min.
Prepared copper-ruthenium-magnesium-aluminium four component catalysts of the present invention can be raw material with biodiesel base crude glycerine moisture, that contain residual alkaline impurities directly, efficient production 1, and the 2-propane diols, concrete reaction process is as follows:
(1), be that 75% biodiesel base crude glycerine solution joins in the stainless steel autoclave that contains the glass beaker liner with 20 milliliters of qualities of glycerin concentration, and in glycerite, add the catalyst after the 1 gram reduction;
(2), with aforesaid reaction vessel sealing, fall air in the reactor with hydrogen exchange, and charge into the hydrogen of certain pressure, the pressure of control hydrogen is at the 20-30 atmospheric pressure;
(3), with reactor place 180 the degree oil bath pans, under stirring condition the reaction 10 hours;
(4), after reaction finishes, reactor is cooled to room temperature, reactant liquor is centrifugal, reclaims catalyst;
(5), the reactant liquor after centrifugal is through rectifying, gets the cut of boiling point at the 187.3-189 degree, confirms back calculating output through gas chromatographic analysis.
Beneficial effect of the present invention is as follows:
Adopt the catalyst of this technology preparation to overcome the shortcoming pockety that infusion process is brought, improved the decentralization and the utilization ratio of metal.This technology provides a kind of novel suitability for industrialized production 1 that can be used for, and the new way of 2-propane diols has been abandoned industrial production 1 in the past, and 2-propane diols productive rate is low, problems such as the high and environmental pollution of cost.
The specific embodiment
Embodiment 1
Get 2.416 gram Cu (NO
3)
23H
2O, 35.84 gram Mg (NO
3)
26H
2O, 18.75 gram Al (NO
3)
39H
2O is dissolved in 400ml water and obtains Cu
2+, Mg
2+, Al
3+Concentration be respectively 0.025,0.35, the saline solution of 0.125mol/L, get 13.25 gram Na
2CO
3, 16 gram NaOH are dissolved in 500ml water and obtain OH
-, CO
3 2-Concentration is respectively 0.8, the alkali lye of 0.25mol/L, adopts the method for co-precipitation, and above-mentioned metal ion solution and alkali lye are added drop-wise in the mixer according to 1/1 ratio, and the temperature of control mixed liquor is 25 degree, and the pH value of mixed liquor is 9-10.Above-mentioned gained sediment was transferred in the flask 120 degree crystallization 20-30 hour, sediment that crystallization is good filter, spend deionised water to pH value of filtrate less than 7, be transferred to baking oven then in 80 degree dried overnight, then that drying is good sample is transferred in the Muffle furnace, in 400 degree roastings 4 hours, 300 degree reduction obtained Cu in 1.5 hours in hydrogen stream again
0.4/ Mg
5.6Al
2O
8.6Catalyst, getting the good catalyst of 1 gram reduction is poured in the glycerine water solution of 8 gram mass concentration 75% immediately, the good seal autoclave, with the air in the hydrogen exchange reactor, charge into the hydrogen of 2MPa then, start and stir heat temperature raising simultaneously, the temperature in the control reactor is 180 degree, reacts 10 hours.After reaction finishes, the reactor cool to room temperature, centrifugal, make reaction product solution and catalyst separation, obtain reactant liquor through the laggard promoting the circulation of qi analysis of hplc of rectifying, calculate glycerol conversion yield and 1, the selectivity of 2-propane diols.The conversion ratio of glycerine is 56.7%, 1, and the selectivity of 2-propane diols is 97.1%.The result gathers and sees Table 1.
Embodiment 2
Get 2.416 gram Cu (NO
3)
23H
2O, 35.84 gram Mg (NO
3)
26H
2O, 18.75 gram Al (NO
3)
39H
2O, 0.1 gram RuCl
3Be dissolved in the 400ml water and obtain saline solution, get 13.25 gram Na again
2CO
3, 16g gram NaOH is dissolved in the alkali lye that 500ml water obtains respective concentration, adopts the method for co-precipitation, and above-mentioned metal ion solution and alkali lye are added drop-wise in the mixer according to 1/1 ratio, and the temperature of control mixed liquor is 25 degree, and the pH value of mixed liquor is 9-10.Above-mentioned gained sediment was transferred in the flask 120 degree crystallization 20-30 hour, sediment that crystallization is good filter, spend deionised water to pH value of filtrate less than 7, be transferred to baking oven then in 80 degree dried overnight, then that drying is good sample is transferred in the Muffle furnace, in 400 degree roastings 4 hours, 300 degree reduction obtained Ru in 1.5 hours in hydrogen stream again
0.02Cu
0.4/ Mg
5.6Al
1.98O
8.57Catalyst, it is in 75% the glycerine water solution that the good catalyst of getting 1 gram reduction is poured into 8 gram mass concentration immediately, the good seal autoclave, with the air in the hydrogen exchange reactor, charge into the hydrogen of 2MPa then, start and stir heat temperature raising simultaneously, the temperature in the control reactor is 180 degree, reacts 10 hours.After reaction finishes, the reactor cool to room temperature, centrifugal, make reaction product solution and catalyst separation, obtain reactant liquor through the laggard promoting the circulation of qi analysis of hplc of rectifying, calculate glycerol conversion yield and 1, the selectivity of 2-propane diols.The conversion ratio of glycerine is 70.6%, 1, and the selectivity of 2-propane diols is 96.1%.The result gathers and sees Table 1.
Table 1 catalyst reaction specific activity
Claims (2)
1. direct hydrogenation preparing 1 of biodiesel base crude glycerine, copper-the ruthenium of 2-propane diols-magnesium-aluminium four component catalysts and preparation method thereof, it is characterized in that: adopt synthetic copper-ruthenium of one step of coprecipitation-magnesium-aluminium four component catalysts, after roasting, reduction, can directly use and be raw material hydrogenation preparing 1 with biodiesel base crude glycerine, in the 2-propane diols, the Preparation of catalysts step is as follows:
(1), prepares the mixed solution of certain density copper nitrate, magnesium nitrate, aluminum nitrate and ruthenic chloride, Cu in the control solution
2+, Mg
2+, Al
3+Concentration be respectively 0.025,0.35,0.125mol/L, Ru
3+Concentration is 0.001mol/L;
(2), the mixed solution (alkali lye) of preparation certain density NaOH and sodium carbonate, control solution O H
-, CO
3 2-Concentration is respectively 0.8,0.25mol/L;
(3), above-mentioned metal ion solution and alkali lye are added drop-wise in the mixer according to 1/1 ratio, the temperature of control mixed liquor is that the pH value of 25 degree, mixed liquor is 9-10;
(4), above-mentioned precipitation was transferred in the flask 120 degree crystallization 20-30 hour;
(5), sediment that crystallization is good filter, spend deionised water to pH value of filtrate less than 7, be transferred to baking oven then in 80 degree dried overnight;
(6), the sample that drying is good was transferred in the Muffle furnace, in 400 degree roastings 4 hours;
(7), before above-mentioned catalyst uses, reduction is 1.5 hours in 300 degree, hydrogen stream, the flow of control hydrogen is at 40ml/min.
2. the direct hydrogenation preparing 1 of biodiesel base crude glycerine according to claim 1, copper-the ruthenium of 2-propane diols-magnesium-aluminium four component catalysts and preparation method thereof, it is characterized in that prepared copper-ruthenium-magnesium-aluminium four component catalysts can be raw material with biodiesel base crude glycerine moisture, that contain residual alkaline impurities directly, efficient production 1, the 2-propane diols, concrete reaction process is as follows:
(1), be that 75% biodiesel base crude glycerine solution joins in the stainless steel autoclave that contains the glass beaker liner with 20 milliliters of qualities of glycerin concentration, and in glycerite, add the catalyst after the 1 gram reduction;
(2), with aforesaid reaction vessel sealing, fall air in the reactor with hydrogen exchange, and charge into the hydrogen of certain pressure, the pressure of control hydrogen is at the 20-30 atmospheric pressure;
(3), with reactor place 180 the degree oil bath pans, under stirring condition the reaction 10 hours;
(4), after reaction finishes, reactor is cooled to room temperature, reactant liquor is centrifugal, reclaims catalyst;
(5), the reactant liquor after centrifugal is through rectifying, gets the cut of boiling point at the 187.3-189 degree, confirms back calculating output through gas chromatographic analysis.
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|---|---|---|---|
| CN2011100629880A CN102188982A (en) | 2011-03-16 | 2011-03-16 | Copper-ruthenium-magnesium-aluminum tetra ingredient catalyst used to prepare 1, 2-propylene glycol through directly adding hydrogen into biodiesel based crude glycerine |
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|---|---|---|---|
| CN2011100629880A CN102188982A (en) | 2011-03-16 | 2011-03-16 | Copper-ruthenium-magnesium-aluminum tetra ingredient catalyst used to prepare 1, 2-propylene glycol through directly adding hydrogen into biodiesel based crude glycerine |
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|---|---|
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|---|---|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010099078A1 (en) * | 2009-02-25 | 2010-09-02 | W. R. Grace & Co.-Conn. | Process for making 1, 2-propane diol from hydrogenation of glycerol |
-
2011
- 2011-03-16 CN CN2011100629880A patent/CN102188982A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010099078A1 (en) * | 2009-02-25 | 2010-09-02 | W. R. Grace & Co.-Conn. | Process for making 1, 2-propane diol from hydrogenation of glycerol |
Non-Patent Citations (4)
| Title |
|---|
| 《Applied Catalysis B: Environmental》 20101020 Zhenle Yuan et. al. "Hydrogenolysis of glycerol over homogenously dispersed copper on solid base catalysts" 第431-440页 , 第101期 * |
| 《南京工业大学学报（自然科学版）》 20101203 钱仲瑛 等 "Pd对Cu/ZnO催化甘油氢解制取1,2-丙二醇性能的影响" 第36-40页 第32卷, 第6期 * |
| ZHENLE YUAN ET. AL.: ""Hydrogenolysis of glycerol over homogenously dispersed copper on solid base catalysts"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 钱仲瑛 等: ""Pd对Cu/ZnO催化甘油氢解制取1,2-丙二醇性能的影响"", 《南京工业大学学报（自然科学版）》 * |
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Application publication date: 20110921 |