CN102675045A - Method for preparing ethylene glycol and 1,2-propylene glycol by using saccharide solution - Google Patents
Method for preparing ethylene glycol and 1,2-propylene glycol by using saccharide solution Download PDFInfo
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Abstract
The invention provides a method for preparing ethylene glycol and 1,2-propylene glycol by using a high-concentration saccharide solution. Reaction raw materials comprise cane sugar, glucose, fructose, fructosan, xylose, soluble lower polyxylose and soluble starch. According to the method, high-concentration saccharide is used as a reaction raw material, and a high-pressure pump feeding mode is used in a reaction process which is performed in a high-pressure reaction kettle; iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum which serve as transition metal in eighth, ninth and tenth groups are used as hydrogenation active ingredients; the hydrogenation active ingredients form a composite catalyst together with metal tungsten, tungsten carbide, tungsten nitride, tungsten phosphide, tungsten oxide, tungsten sulfide, tungsten chloride, tungsten hydroxide, tungsten bronze, tungstic acid, tungstate, metatungstic acid, metatungstate, paratungstic acid, paratungstate, peroxotungstic acid, peroxotungstate and tungsten-containing heteropolyacid which serve as catalytic active ingredients; and the high-concentration saccharide solution can be efficiently prepared into the ethylene glycol and the propylene glycol at high selectivity and high yield in a one-step catalytic conversion process under the hydrothermal condition that the temperature is 120 to 300 DEG C and the hydrogen pressure is 1 to 13MPa. By the method, the problem of coking of the high-concentration saccharide in the catalytic conversion process can be effectively solved, and high-concentration ethylene glycol and propylene glycol can be prepared by the high-concentration saccharide.
Description
Technical field
The present invention relates to a kind of sugar soln preparing ethylene glycol, 1, the method for 2-Ucar 35, specifically high concentration sugar solution is through step shortening degraded preparing ethylene glycol, 1, the reaction process of 2-Ucar 35.
Background technology
Terepthaloyl moietie, Ucar 35 are the important energy liquid fuels; It also is very important polyester synthesis material; For example, be used for polyethyleneterephthalate (PET), PEN (PEN); Can also be used as frostproofer, lubricant, softening agent, tensio-active agent etc., be broad-spectrum petrochemical complex basic material.
At present, the industrial production of terepthaloyl moietie mainly is to adopt the petroleum route, promptly obtains oxyethane behind the ethylene epoxidizing; Hydration obtains terepthaloyl moietie [document 1: Cui Xiaoming, domestic and international terepthaloyl moietie production development overview, chemical industry then; 2007,25, (4); 15-21. document 2:Process for preparing ethanediol bycatalyzing epoxyethane hydration, Patent No.CN1463960-A; CN1204103-C].Compound method depends on non-renewable petroleum resources, and comprises selective oxidation or epoxidation step in the production process, and technical difficulty is big, and efficient is low, and by product is many, and material consumption is high and seriously polluted.
The biomass that utilization has recyclability prepare terepthaloyl moietie, 1, and the 2-Ucar 35 can reduce human dependence to the fossil energy material, helps realizing environmental friendliness and sustainable economic development.Glucose, sucrose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides are widespread in nature.Along with agrotechnical development, its output is growing.Development prepares terepthaloyl moietie, Ucar 35 with sugar compounds, not only can reduce the dependence to petroleum resources to a certain extent, simultaneously, helps to realize deep processing of farm products system high added value chemical.At present; Technology [document 3:Process for the preparationof lower polyhydric alcohols with glycosyl compound system polyvalent alcohol; Patent; No.US5107018. document 4:Preparation oflower polyhydric alcohols; Patent, No.US5210335 document 5: a kind of novel process of producing terepthaloyl moietie, CN200610068869.5 document 6: a kind of method of producing divalent alcohol and polyvalent alcohol by cracking sorbierite; CN200510008652.0] generally comprise three steps: (1) starch obtains glucose (2) glucose through gelatinization, enzyme liquefaction, enzyme glycolysis process and obtains sorbyl alcohol (3) sorbyl alcohol hydrogenolysis generation product polyvalent alcohol under HTHP through noble ruthenium or nickel catalyzator hydrogenation, is mainly Ucar 35, USP Kosher, terepthaloyl moietie.Wherein, the yield of terepthaloyl moietie is in the 10-30% scope.Reaction process is loaded down with trivial details.An other preparation approach is to transform preparation of cellulose terepthaloyl moietie [document 4:Direct catalytic conversion of cellulose into ethylene glycol using nickel-promotedtungsten carbide catalysts through shortening under the hydrothermal condition; Angew.Chem.Int.Ed.2008; 47,8510-8513.Document 5:transition metal-tungsten bimetallic catalysts for the conversion of cellulose intoethylene glycol, ChemSusChem 2010,3,63-66].This method is with tungsten carbide catalyst, and perhaps the promoted tungsten catalyzer of transition metal carries out catalyzed conversion to Mierocrystalline cellulose, thereby obtains terepthaloyl moietie.The terepthaloyl moietie yield can reach 60-75%.Equally can catalysis glucose under this catalyst system, saccharide compound such as fructose transforms, highly selective obtains terepthaloyl moietie, Ucar 35 [document 6: a kind of method of preparing ethanediol from polyhydroxy compounds, CN200810229065.8].Yet in the reaction process of being reported in the document 5,6, the reaction density of glycogen material is 1wt%, and the concentration of glycol product is lower, and aqueous solvent accounts for the 99wt% of reaction back solution.Because the product of terepthaloyl moietie, Ucar 35 adopts the distillatory method to separate in the Industrial processes.The terepthaloyl moietie boiling point is 197.5 ℃, 1, and 2-Ucar 35 boiling point is 188.2 ℃.Thereby the low energy with labor of production concentration is used for still-process.For improving the economy of reaction process, reduce the distillation energy consumption, the concentration that improves product in the reaction process is most important.
Summary of the invention
The object of the present invention is to provide a kind of sugar soln to prepare the method for terepthaloyl moietie, Ucar 35.Sugar soln is sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides, Zulkovsky starch solution.Through a step shortening degradation process, high yield, highly selective prepare terepthaloyl moietie.
For realizing above-mentioned purpose; The technical scheme that the present invention takes is: with sugar soln (concentration is greater than 5wt%); Comprise that sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides, Zulkovsky starch are reaction raw materials, solvent is water or C1-C6 alcohols or its mixing solutions.Adopt liquid high pressure pump feeding manner in the reaction process; Before charging; At the bottom of still, add a certain amount of catalyzer and solvent in advance; The amount of solvent can be as the criterion by smooth stirring with the catalyst solid active ingredient, and specifically quantity of solvent can the immersion solid catalyzer and less than 1/3 of reactor volume.In reaction process, the amount of employed catalyzer is the catalytic amount that realization response is carried out smoothly in the reaction system.
Catalyzer comprises catalytic active component A and catalytic active component B, and active component A and active ingredient B can be supported on the common carrier, also can constitute mixed catalyst with the form of mechanically mixing; Catalytic active component A comprises one or more in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families, and catalytic active component B comprises one or more in mineral compound, organic cpds, complex compound and the metal simple-substance of tungsten; Specifically comprise in the oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxide tungstate, heteropoly tungstic acid of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of carbide, nitride, phosphide, the tungsten of tungsten, tungsten one or more; Before charging, in reaction kettle, add catalyzer, the catalyzer that adds in advance comprises catalytic active component A; If catalytic active component B is a solid, it also adds in the reaction kettle with catalytic active component A equally in advance; If catalytic active component B is a liquid, can before charging, all or partly add reaction kettle in advance, also can all or partly add by pump with the reaction raw materials sugar soln; Stirring reaction in reaction kettle; Filling hydrogen in the reaction kettle before the reaction, temperature of reaction is higher than 120 ℃, and thermolysis does not take place with raw material and product and is as the criterion in upper temperature limit.Reaction times is no less than 5 minutes.More preferably the original pressure during the hydrogen room temperature is 1-12MPa in the reaction kettle, and more preferably temperature of reaction is 120-300 ℃, and the reaction times is no less than 5 minutes; Preferred temperature of reaction is 180-250 ℃, the more preferably original pressure 3-7MPa of hydrogen in the reaction kettle under the room temperature.
The metal active composition of active component A and catalytic active component B (in tungsten weight) weight ratio is between 0.02-3000 times of scope in the catalyzer.Preferred weight ratio is between 0.1-100 times of scope.
Generated by glycosyl compound in the reaction process of terepthaloyl moietie, the middle species of generation are undersaturated alcohol aldehyde, thereby need just can obtain final polyvalent alcohol through the shortening process.Thereby, need have the active component A of shortening ability in the catalyzer.Catalytic active component can be supported on the carrier, comprises gac, aluminum oxide, silicon oxide, silit, zirconium white, zinc oxide, one or more complex bodys of titanium oxide.The loading of metal is at 0.05-50wt%, preferably at 0.5-30wt%.Perhaps catalytic active component A is with the skeleton metal catalyst of active ingredient as catalyst backbone, for example Raney's nickel etc.
Active ingredient B in the catalyzer is one or more in mineral compound, organic cpds, complex compound and the metal simple-substance of tungstenic, comprises in the oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxide tungstate, heteropoly tungstic acid of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of carbide, nitride, phosphide, the tungsten of tungsten, tungsten one or more.In reaction process, the tungsten species in the catalyzer have important katalysis for the catalyzed degradation of polyol.
Active component A and active ingredient B can be supported on the common carrier, also can constitute hybrid catalyzer with the form of mechanically mixing.
When being reaction raw materials with high concentration sugar solution; Because side reactions such as polymerization take place in high concentration sugar reaction raw materials easily under the pyritous reaction conditions; Thereby the inhibition catalyst activity finally causes preparing the termination of terepthaloyl moietie, Ucar 35 reaction, so must adopt special technological process pointedly; Suppress side reaction and take place, improve the selectivity of goal response.In the method for the invention, high concentration sugar solution reaction raw material adopts the charging of liquid high pressure pump mode, in reaction process, constantly joins in the reaction kettle.Before charging; At the bottom of still, be added with a certain amount of catalyzer and solvent in advance; The amount of solvent can be as the criterion by smooth stirring with the catalyst solid active ingredient, and solvent plays the dispersion agent effect of catalyzer and reactant, avoids reaction raw materials sugar excessive concentration to cause phenomenon generations such as polymerization coking.Solvent should have thermostability under temperature of reaction, can be water, alcohols.Be reflected under the agitation condition and carry out.In high concentration sugar raw material fill process; The glycogen material at first is left on the solvent cut of Polycondensation Reactor and Esterification Reactor; Sugar after the dilution is consumed by catalyzed conversion constantly; Make the sugared concentration in the reaction kettle in reaction process, remain at lower concentration level, promptly in reaction, reaction raw materials concentration is carried out differential, and the concentration of product is realized integration.Through the technique means that the present invention adopted; Not only can successfully solve the polymerization coking problem of high concentration sugar, simultaneously, with respect to the mode of one-time pad glycogen material; Owing to improved the molar ratio of catalyzer and reactant in the reaction process; Thereby suppressed the side reaction generation, improved the selectivity of title product, had significant effect.
The concentration of reaction raw materials sugar soln is 5wt%-90wt%.
Below listed embodiment carry out in the autoclave, can pass through reactor design optimization but do not get rid of, for example, the placed in-line form of employing multi-stage reacting kettle, or paste state bed reactor realize that sugared reaction raw materials reacts fully, obtain better reaction result.
Advantage of the present invention: with high concentration sugar solution is reaction raw materials; Comprise that glucose, sucrose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides, Zulkovsky starch are feedstock production terepthaloyl moietie, Ucar 35; With respect to existing glycosyl biomass-making polyvalent alcohol technology, have reactant concn height, reaction process easiness in handling, terepthaloyl moietie, the remarkable advantage that the Ucar 35 product concentration is high, yield is high; Can reduce the distillation energy consumption of reaction product greatly, improve the economy of reaction process.
The present invention provides a kind of high concentration sugar solution catalyzing to transform the method for preparing ethylene glycol, Ucar 35, and the concentration of reaction raw materials sugar soln is 5wt%-90wt%.Reaction process is controlled easily, and terepthaloyl moietie in the product, the Ucar 35 yield is high, concentration is high, can reduce product distillation cost significantly.
Through specific embodiment the present invention is elaborated below, but these embodiment do not constitute restriction to content of the present invention.
Embodiment
Embodiment 1
The preparation of metal catalyst Ru/AC: with ruthenium trichloride aqueous solution impregnated activated carbon carrier, behind 120 ℃ of dry 12h, in 500 ℃ of nitrogen atmosphere, reduce 1h, obtain catalyzer Ru/AC (2wt%Ru).
Embodiment 2
The preparation of metal catalyst W/AC: with ammonium metatungstate aqueous solution impregnated activated carbon carrier, behind 120 ℃ of dry 12h, in 700 ℃ of nitrogen atmosphere, reduce 1h, obtain catalyzer W/AC (30wt%W).
Embodiment 3
Ni-W
2The C/AC Preparation of Catalyst: reference Angew.Chem.Int.Ed.2008,47,8510-8513 is that 15: 1 ratio is processed mixing solutions with metatungstic acid ammonia and nickelous nitrate according to tungsten/nickel weight ratio, wherein, the mass and size concentration of metatungstic acid ammonia is 0.4g/ml.Then, with mixing solutions Immesion active carbon carrier (AC).Behind 120 ℃ of oven drying 12h, catalyst precursor is placed H
2Carry out temperature programming carbon thermal response in the atmosphere, concrete reaction process is: the 2.0g precursor is warming up to 400 ℃ by room temperature 1h in crystal reaction tube, then is warming up to 700 ℃ and keep 1h to carry out carbonization with 1 ℃/min, and hydrogen flow rate is 100ml/min.Obtaining the tungsten loading is that 30wt%, nickel loading are the Ni-W of 2wt%
2The C/AC catalyzer is expressed as Ni-W
2C/AC (2wt%Ni-30wt%W
2C).
Embodiment 4
Pd-W
2The C/AC Preparation of Catalyst: method is with embodiment 3, and difference is to substitute nickel nitrate solution with palladium chloride solution, and obtaining the tungsten loading is that 30wt%, palladium loading are the Pd-W of 5wt%
2The C/AC catalyzer is expressed as Pd-W
2C/AC (5wt%Pd-30wt%W
2C).
Embodiment 5
HPP feeding manner catalyzed conversion experiment: with 0.33g catalyzer (0.15g Ru/AC 5wt%; 0.18gW/AC 30wt%) join in the 300ml reaction kettle with 30ml water; After feeding three gases of hydrogen exchange, fill hydrogen, be warming up to 240 ℃ under the agitation condition to 5MPa.After question response still temperature is warming up to 240 ℃, feed in the reaction kettle with certain speed, begin reaction with the sugar soln of high-pressure liquid phase pump with 50wt% concentration.After the charging of question response raw material finishes, prolong the 60min reaction.After reaction finishes, reduce to room temperature, get the supernatant liquid after centrifugal, on performance liquid chromatography calcium type ion exchange column, separate and detect with differential refractometer detector.Only to title product terepthaloyl moietie, 1,2-Ucar 35 and hexavalent alcohol (comprising sorbyl alcohol, N.F,USP MANNITOL) calculate in the product yield, and other product liquids comprise butantetraol, ethanol, not principal component, and gaseous product (CO
2, CH
4, C
2H
6Deng) do not calculate its yield.
The comparative example 1
A charging method catalyzed conversion experiment: with 5.0g sugar, 0.33g catalyzer and 100ml water join in the 300ml reaction kettle, behind three gases of feeding hydrogen exchange, fill hydrogen to 5Mpa, are warming up to 240 ℃ under the agitation condition, reaction 2h.Reduce to room temperature, get product liquid analysis.Analytical procedure is as embodiment 5.
Embodiment 6
HPP feeding manner catalyzed conversion experiment involved in the present invention contrasts with a charging method catalyzed conversion result of experiment of open source literature.
The catalyzed conversion result contrast of table one the present invention and publication and literature method
Annotate:
aThe reaction raw materials mean concns is for after the liquor pump charging finishes, and sugar soln joins the glycogen material overall average concentration in the reaction kettle that leaves a certain amount of solvent in advance.
bThe amount of wolframic acid is 0.05g, and the amount of Ru/AC is 0.15g.
cCatalyst levels 0.15g Ru/AC 5wt%, 0.18g W/AC 30wt%.
Can find out from above result, adopt the pump feeding manner, when being raw material with glucose, main highly selective generates terepthaloyl moietie, and the productivity ratio of terepthaloyl moietie and Ucar 35 is 10: 1; And when being raw material with sucrose or fructose, 1, the yield of 2-Ucar 35 increases substantially, and the productivity ratio of terepthaloyl moietie and Ucar 35 was respectively 1: 1 or 1: 6.
The yield of resulting terepthaloyl moietie of pump feeding manner and Ucar 35 is significantly higher than once the directly result of the reaction of charging, and the total recovery of terepthaloyl moietie and Ucar 35 can improve more than 1 times, and effect is remarkable.
Obviously, method provided by the present invention can be used in the high concentration sugar catalytic material and transforms preparing ethylene glycol and Ucar 35, and the yield of product and selectivity are high, have significant technical progress with respect to existing method.
Embodiment 7
The conversion results of different concns glucose under the liquor pump feeding manner
Except glucose solution concentration difference, reaction conditions is with embodiment 4.When sugar soln concentration is higher than 50wt%, adopt the hot water solvent to improve the solubleness of sugar.
The conversion results of different concns glucose under the table two liquor pump feeding manner
Annotate:
aThe reaction raw materials mean concns is for after the liquor pump charging finishes, and sugar soln joins the glycogen material overall average concentration in the reaction kettle that leaves a certain amount of solvent in advance.
Claims (10)
1. a sugar soln prepares terepthaloyl moietie, 1, and the method for 2-Ucar 35 is characterized in that: is reaction raw materials with concentration greater than 5 wt% sugar solns, carries out catalytic hydrogenation reaction in closed reaction kettle, adopts the pressure liquid pump feeding manner in the reaction process; Before charging, in reaction kettle, add catalyzer and solvent, the amount of solvent can be as the criterion by smooth stirring with catalyzer; Be reflected under the agitation condition and carry out;
The catalyzer that is adopted comprises catalytic active component A and catalytic active component B, and active component A and active ingredient B both can be supported on the common carrier, also can in reaction process, the form with mechanically mixing constitute mixed catalyst; Catalytic active component A comprises a kind of in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families with Catalytic Hydrogenation Properties or more than two kinds, and catalytic active component B comprises one or more in mineral compound, organic cpds, complex compound or the tungsten simple substance of tungsten;
Before charging, in reaction kettle, add catalyzer, the catalyzer that adds in advance comprises catalytic active component A; Simultaneously, if catalytic active component B is a solid, it also adds in the reaction kettle with catalytic active component A equally in advance; If catalytic active component B is a liquid, can before charging, all or partly add reaction kettle in advance, also can all or partly add by pump with the reaction raw materials sugar soln;
In the reaction kettle stirring reaction; Filling hydrogen in the reaction kettle before the reaction, temperature of reaction >=120 ℃, the reaction times is no less than 5 minutes;
In use, the activeconstituents of the metal active composition of activity of such catalysts component A and catalytic active component B (in tungsten weight) weight ratio is 0.02-3000:1.
2. according to the described method of claim 1, it is characterized in that: the solvent that Polycondensation Reactor and Esterification Reactor adds in advance is water or C1-C6 alcohols or the mixing solutions more than two kinds in them, and its add-on can the immersion solid catalyzer and less than 1/3 of reactor volume;
In reaction process, the amount of employed catalyzer is the catalytic amount that realization response is carried out smoothly in the reaction system.
3. according to the described method of claim 1, it is characterized in that: catalytic active component B is one or more in the oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxide tungstate, heteropoly tungstic acid of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of carbide, nitride, phosphide, the tungsten of tungsten, tungsten.
4. according to the described method of claim 1, it is characterized in that: filling hydrogen in the reaction kettle before the reaction, the original pressure of hydrogen is 1-12MPa during room temperature; Temperature of reaction >=120 ℃, thermolysis does not take place with product and is as the criterion in upper temperature limit.
5. according to claim 1 or 4 described methods, it is characterized in that: temperature of reaction 120-300 ℃, preferred temperature of reaction is 180-250
oC; The original pressure 3-7 MPa of preferred hydrogen in the reaction kettle under the room temperature.
6. according to the described method of claim 1, it is characterized in that:
Said catalytic active component A also can be that the skeleton metallic forms exists;
Or said catalytic active component A is supported on the carrier, and said carrier is gac, aluminum oxide, silicon oxide, silit, zirconium white, zinc oxide, titanium oxide is a kind of or the complex carrier more than two kinds; The content of activity component metal on catalyzer is at 0.05-50 wt%.
7. according to the described method of claim 6, it is characterized in that: the loading of said activity of such catalysts component A is preferably at 0.5-30 wt%.
8. according to the described method of claim 1, it is characterized in that: the concentration of reaction raw materials sugar soln is 10wt%-90wt%; Catalyst consumption is a catalytic amount.
9. according to the described method of claim 1, it is characterized in that: the metal active composition of said catalyst activity component A and catalytic active component B (calculating with tungsten weight) preferred weight ratio in use is 0.1-100:1.
10. according to the described method of claim 1, it is characterized in that: said sugar soln is a kind of or solution more than two kinds in sucrose, glucose, fructose, Polylevulosan, wood sugar, solubility xylooligosaccharides, the Zulkovsky starch; Solvent is water or C1-C6 alcohols or the mixing solutions more than two kinds in them.
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