CN102731255B - Method for preparing glycol by using corncobs as raw materials - Google Patents
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Abstract
The invention provides a method for preparing glycol by using corncobs as raw materials, characterized by using corncobs as raw materials, conducting steam explosion or attenuant acid hydrolysis, then using a strongly alkaline aqueous solution to immerse, then rinsing with clear water to obtain a cellulosic material, and placing the cellulosic material under the catalytic hydrogenation reaction conditions to prepare glycol, wherein in the catalytic reaction, the preparation of glycol with high yield is realized by using metal or metal tungsten oxide thereof of cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum and a compound containing tungsten or elemental tungsten as a catalyst and conducting one-step catalytic conversion at the temperature of no lower than 150 DEG C under the hydrothermal condition of the hydrogen pressure being 0.1-15 MPa. The conversion process aiming at biomass material corncobs provided by the invention has the significant advantages of simple and practical pretreatment method, and high yield of conducting catalytic conversion to prepare glycol.
Description
Technical field
The present invention relates to a kind of method of preparing ethylene glycol, is specifically the method that raw material is prepared ethylene glycol by corn cob.
Background technology
Ethylene glycol is important large Essential Chemistry product, and within 2010, global ethylene glycol output reaches more than 2,000 ten thousand tons, and wherein, 80% is synthetic for PET resin, and 12% is synthetic for deicing fluid, and about 8% for other chemical intermediates.The existing industrial product route of ethylene glycol is mainly to depend on oil ethene resource.Utilizing reproducible biomass resource synthesizing glycol technology is one of important channel of realizing fossil energy substitution of resources [document 1:Process for the preparation of lower polyhydric alcohols, patent, No.US5107018. document 2:Preparation of lower polyhydric alcohols, patent, No.US5210335. document 3: a kind of novel process of producing ethylene glycol, CN200610068869.5. document 4: a kind of method of being produced dibasic alcohol and polyvalent alcohol by cracking sorbierite, CN200510008652.0].
2008, the scientific research personnel of the Dalian Chemistry and Physics Institute studies discovery first, Mierocrystalline cellulose can obtain ethylene glycol [document 5:Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts by direct catalyzed conversion highly selective, Angew.Chem.Int.Ed.2008,47,8510-8513.Document 6:transition metal-tungsten bimetallic catalysts for the conversion of cellulose into ethylene glycol, ChemSusChem 2010,3,63-66.Document 7:A new 3Dmesoporous carbon replicated from commercial silica as acatalyst support for direct conversion of cellulose into ethylene glycol, Chem.Commun., 2010,46,862-864.].In research, adopted pure Microcrystalline Cellulose, the yield of ethylene glycol reaches 60-75%.But the Mierocrystalline cellulose of occurring in nature is always present in plant materials, together with being woven with the complexity such as hemicellulose, xylogen composition.Therefore, utilize full biomass Mierocrystalline cellulose directly to transform preparing ethylene glycol, can be in the impact that is subject in varying degrees these components.Research is found, while carrying out catalyzed conversion taking maize straw as raw material, the yield of ethylene glycol and the preprocessing process of raw material have very large relation [document 8:Catalytic Hydrogenation of Corn Stalk to Ethylene Glycol and 1,2-Propylene Glycol, Ind.Eng.Chem.Res.2011,50,6601-6608].Because weave construction and composition formation that different plant materials has are had nothing in common with each other, therefore, need to develop pointedly full biomass cellulosic material pretreatment process and catalytic reaction process, to obtain best ethylene glycol yield.
In corn cob, contain abundant hemicellulose, Mierocrystalline cellulose and a certain amount of xylogen.Contained hemicellulose can extract and produce chemical and the healthcare products such as butanols, furfural, xylo-oligosaccharide, Xylitol for the process such as biological fermentation, catalyzed conversion through certain method.And the raw material of remaining rich cellulose, can be used for catalyzed conversion produce ethylene glycol.Thereby the corn cob base Mierocrystalline cellulose of development simple and effective is prepared ethylene glycol and is had important using value.
Summary of the invention
The invention provides a kind of method by corn cob catalyzed conversion preparing ethylene glycol.
Corn cob raw material is after water vapor explosion treatment or dilute acid hydrolysis, and corn cob strong alkaline aqueous solution immersion treatment, then pass through clear water rinsing to neutral, is placed under catalytic hydrogenation reaction condition and prepares ethylene glycol.
Corn cob water vapor explosion treatment process is for to be placed in autoclave by corn cob, in autoclave, pass into high-temperature high-pressure steam, pressure is 0.5-2.0MPa, and pressure hold time is 0.5-20min, temperature is 160-220 DEG C, then suddenly discharges the pressure of autoclave to normal pressure.
The water content of corn cob, at 25-60%, is 5-60%v/v in the charge amount of steam explosion reactor, and the pressure that suddenly discharges autoclave refers within 0.001 second to 5 seconds and makes autoclave internal pressure be down to normal pressure.
Corn cob dilute acid hydrolysis, temperature is normal temperature (0-30 DEG C)-180 DEG C, diluted acid volumetric molar concentration is 0.02-0.6mol/L, acid comprises one or more in hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, acetic acid, formic acid, time is 5min-24h, and the mass ratio of corn cob raw material and acid solution is 1: 1-1: 100.When hydrolysis temperature is during higher than 100 DEG C, preprocessing process carries out in airtight still, and pressure is corresponding autogenous pressure at this temperature.
Strong alkaline aqueous solution is the alkali metal hydroxide aqueous solution of mass concentration 0.1-15wt%; The mass ratio of corn cob and alkaline solution is 1: 1-1: 50; At 10-80 DEG C, soak 30min-48h.
In strong alkaline aqueous solution, contain the alkali metal hydroxide of mass concentration 0.3-5wt%, the mass ratio of raw material and alkaline solution is 1: 10, and strong alkaline substance is preferably sodium hydroxide; At 20-50 DEG C, soak 1-24h.
Catalytic hydrogenation reaction process is carried out under agitation condition in closed pressure vessel, temperature of reaction >=150 DEG C, hydrogen pressure 0.1-15MPa in reaction process, the mass content of reactant in the aqueous solution is 1-30wt%, reaction times is no less than 5min, in catalyzer used, contain the active component A with shortening function and the tungstenic active ingredient B with catalyse cellulose degradation function, consumption is catalytic amount; In use, the metal active composition of catalyst A and the activeconstituents of catalyst B (with tungsten weighing scale) weight ratio are between 0.02-3000 times of scope.
In catalyzer used, contain the active component A with shortening function and the tungstenic active ingredient B with catalyse cellulose degradation function; Active component A comprises one or more metal or the metal oxide in cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum; The active ingredient B of tungstenic comprises the various compounds of tungsten simple substance and tungsten, comprises specifically one or more in the oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxotungstate, heteropoly tungstic acid of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of wolfram varbide, tungsten nitride, tungsten phosphide, the tungsten of tungsten, tungsten.
Described catalyst activity component A and active ingredient B can be supported on porous support jointly, also can be supported on individually separately and on porous support, form composite catalyst, described carrier is one or two or more kinds complex carrier of gac, aluminum oxide, silicon oxide, silicon carbide, zirconium white, zinc oxide, titanium dioxide; The content of activity component metal on catalyzer is at 0.05-60wt%;
Or described catalyst activity component A also can be with unsupported form Individual existence; Or described catalyst activity B component also can be with unsupported form Individual existence;
In use, the metal active composition of catalyst A and the activeconstituents of catalyst B (with tungsten weighing scale) weight ratio are between 0.1-10 times of scope.
Range of reaction temperature is at 150-350 DEG C, preferred temperature of reaction is 220-280 DEG C, the pressure 3-10MPa of preferred hydrogen in reaction process, the preferred reaction time is 30min-3h, quality (taking the active metal quality) ratio of reaction raw materials and catalyzer is as 1: 1-30000: 1.The quality of reaction raw materials and catalyzer (taking active metal quality) is 3 than preferable range: 1-3000: 1, and preferred scope is 4: 1-1000: 1.
Catalytic hydrogenation reaction device adopts closed pressure vessel, comprises intermittent reaction autoclave reactor, semibatch reaction tank reactor, slurry state hearth reactor, circulating fluid bed type reactor.
The effect that the present invention is useful
Taking corn cob as raw material,, realize corn cob base lignocellulosic material and be converted into high yield ethylene glycol in conjunction with catalytic reaction process through simple and easy to do pretreatment mode.
Embodiment
Embodiment 1
Get corn cob powder (20-40 order) 10kg, adding water and making its water content is 30wt%, is placed in 160 DEG C of steam explosion reactors, in 60 seconds of (pressure 1.0MPa) constant voltage, then carries out steam explosion operation.To the 8kg solid residue (dry weight) obtaining, add the NaOH aqueous solution of 50kg concentration 1wt% to it, at 25 DEG C of room temperatures, soak 12h, then clear water rinsing, to neutral, obtains 6kg (dry weight) cellulosic material.
Embodiment 2
Get corn cob powder (10-20 order) 10kg, adding water and making its water content is 45wt%, is placed in 30 seconds of 180 DEG C of steam explosion reactors (pressure 1.2MPa) constant voltage, then carries out steam explosion operation.To the 7.5kg solid residue (dry weight) obtaining, add the NaOH aqueous solution of 15kg concentration 5wt% to it, at 20 DEG C of room temperatures, soak 6h, then clear water rinsing, to neutral, obtains 5.8kg (dry weight) cellulosic material.
Embodiment 3
Get corn cob powder (40-60 order) 10kg, adding 50kg volumetric molar concentration is the diluted hydrochloric acid aqueous solution of 0.03mol/L, airtight 140 DEG C of hydrolysis 6 hours that are heated to.Then, centrifugally filter out solid insoluble, under room temperature, soak 12 hours then centrifugation solid insoluble with the sodium hydroxide solution of concentration 2wt% according to solid and the solution weight ratio of 1: 10, to neutral, obtain 5.0kg (dry weight) cellulosic material with clear water rinsing.
Embodiment 4
Get corn cob powder (40-60 order) 10kg, adding 50kg volumetric molar concentration is the diluted hydrochloric acid aqueous solution of 0.3mol/L, airtight 80 DEG C of hydrolysis 2 hours that are heated to.Then, centrifugally filter out solid insoluble, under room temperature, soak 12 hours then centrifugation solid insoluble with the sodium hydroxide solution of 10wt% according to solid and the solution weight ratio of 1: 1, to neutral, obtain 4.8kg (dry weight) cellulosic material with clear water rinsing.
Embodiment 5
Get respectively the Mierocrystalline cellulose sample that 5.0g handles well according to embodiment 1,2, add 100ml water, 0.1g wolframic acid, 5%Ru/AC catalyzer 0.1g, in autoclave, 250 DEG C are reacted 2h, are filled with 5Mpa hydrogen before reaction, 500 revs/min of stirring velocitys.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains are opened in pressure release, after product is accurate qualitative with chromatograph-mass spectrometer, with liquid-phase chromatographic analysis polyvalent alcohol product yield.
Embodiment 6
Get respectively the Mierocrystalline cellulose sample that 5.0g handles well according to embodiment 3,4, add 100ml water, 0.25g 5%Ni-30%W
2c/AC tungsten carbide catalyst, in autoclave, 240 DEG C are reacted 1h, are filled with 5Mpa hydrogen before reaction, 500 revs/min of stirring velocitys.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
Comparative example 1
Get 10kg corn cob powder (20-40 order), adding water and making its water content is 30wt%, be placed in 60 seconds of 160 DEG C of steam explosion reactors (pressure 1.0MPa) constant voltage, then carrying out steam explosion operation carries out after water vapor explosion treatment, then clear water rinsing, to neutral, obtains 8kg (dry weight) cellulose solids residuum.
Get the Mierocrystalline cellulose sample that 5.0g handles well, add 100ml water, 0.1g wolframic acid, 5%Ru/AC catalyzer 0.1g, with in autoclave 250 DEG C react 2h, before reaction, be filled with 5Mpa hydrogen, 500 revs/min of stirring velocitys.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
Comparative example 2
Get 7kg corn cob powder (20-40 order), add the NaOH aqueous solution of 50kg concentration 1wt% to it, at 25 DEG C of room temperatures, soak 12h, then clear water rinsing, to neutral, obtains 6kg (dry weight) cellulose solids residuum.
Get the Mierocrystalline cellulose sample that 5.0g handles well, add 100ml water, 0.1g wolframic acid, 5%Ru/AC catalyzer 0.1g, with in autoclave 250 DEG C react 2h, before reaction, be filled with 5Mpa hydrogen, 500 revs/min of stirring velocitys.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
Comparative example 3
Get corn cob powder (40-60 order) 10kg, adding 50kg volumetric molar concentration is the diluted hydrochloric acid aqueous solution of 0.03mol/L, airtight 140 DEG C of hydrolysis 6 hours that are heated to.Then centrifugally filter out solid insoluble, to neutral, obtain cellulosic material with clear water rinsing.
Get 5.0g Mierocrystalline cellulose sample, add 100ml water, 0.25g 5%Ni-30%W2C/AC tungsten carbide catalyst, in autoclave, 240 DEG C are reacted 1h, are filled with 5Mpa hydrogen before reaction, 500 revs/min of stirring velocitys.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
Comparative example 4
Get the undressed corn cob powder of 5.0g (20-40 order), add 100ml water, 0.1g wolframic acid, 5%Ru/AC catalyzer 0.1g, with in autoclave 250 DEG C react 2h, before reaction, be filled with 5Mpa hydrogen, 500 revs/min of stirring velocitys.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
Comparative example 5
Change corn cob into maize straw, carry out pre-treatment according to the condition water vapour explosion that embodiment 1 is identical in conjunction with dilute alkaline soln, obtain cellulosic material.Afterwards, carry out catalytic conversion reaction according to the condition of embodiment 5, use liquid-phase chromatographic analysis polyvalent alcohol product yield with the cellulosic material of gained.
Comparative example 6
Change corn cob into broomcorn straw, carry out pre-treatment according to the condition water vapour explosion that embodiment 3 is identical in conjunction with dilute alkaline soln, obtain cellulosic material.Afterwards, carry out catalytic conversion reaction according to the condition of embodiment 6, use liquid-phase chromatographic analysis polyvalent alcohol product yield with the cellulosic material of gained.
Embodiment 7
Under embodiment 5,6 and comparative example's 1,2,3,4 conditions, cellulosic material catalyzed conversion result comparative result.As shown in Table 1.
The corn cob catalytic material of table one, various condition processing transforms the reaction result comparison of preparing ethylene glycol
Can see from the listed result of above form, the processing of steam explosion combined alkali, and the cellulose biomass raw material of diluted acid combined alkali processing, can be catalytically conveted to high yield ethylene glycol, reach 65%, be significantly higher than that simple steam explosion is processed and simple alkaline purification after the yield of catalyzed conversion preparing ethylene glycol of cellulosic material, and the conversion of reaction raw materials is more thorough.
Embodiment 8
The catalyzed conversion result comparison of maize straw and sorghum stalk in the cellulosic catalyzed conversion result of corn cob and comparative example 5,6 in embodiment 5,6, as shown in Table 2.
The reaction result comparison of table two, different cellulosic material catalyzed conversion preparing ethylene glycols
Can be seen by the result contrast in form, this reaction process has good selectivity and yield to the conversion preparing ethylene glycol of corn cob.And for other biological raw material maize straw and sorghum stalk, different due to raw material mix and composition and corn cob, even after identical preprocessing process, the catalytic effect in reaction does not have the ideal of corn cob raw material.
Claims (10)
1. a method of preparing ethylene glycol taking corn cob as raw material, is characterized in that: corn cob raw material is after dilute acid hydrolysis, and corn cob strong alkaline aqueous solution immersion treatment, then pass through clear water rinsing to neutral, is placed under catalytic hydrogenation reaction condition and prepares ethylene glycol;
Catalytic hydrogenation reaction process is carried out under agitation condition in closed pressure vessel, temperature of reaction >=150 DEG C, hydrogen pressure 0.1-15 MPa in reaction process, the mass content of reactant in the aqueous solution is 1-30wt%, reaction times is no less than 5 min, in catalyzer used, contain the active component A with shortening function and the tungstenic active ingredient B with catalyse cellulose degradation function, consumption is catalytic amount; In use, the metal active composition of catalyst A and the activeconstituents weight ratio of catalyst B are between 0.02-3000 times of scope, and wherein the weight of B activeconstituents is with tungsten weighing scale.
2. in accordance with the method for claim 1, it is characterized in that: corn cob dilute acid hydrolysis, temperature is normal temperature-180 DEG C, diluted acid volumetric molar concentration is 0.02-0.6 mol/L, acid comprises one or more in hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, acetic acid, formic acid, time is 5min-24 h, and the mass ratio of corn cob raw material and acid solution is 1:1-1:100.
3. it is characterized in that in accordance with the method for claim 1: strong alkaline aqueous solution is the alkali metal hydroxide aqueous solution of mass concentration 0.1-15wt%; The mass ratio of corn cob and alkaline solution is 1:1-1:50; At 10-80 DEG C, soak 30 min-48 h.
4. in accordance with the method for claim 1, it is characterized in that: in strong alkaline aqueous solution, contain the alkali metal hydroxide of mass concentration 0.3-5wt%, the mass ratio of raw material and alkaline solution is 1:10; At 20-50 DEG C, soak 1-24 h.
5. it is characterized in that in accordance with the method for claim 4: strong alkaline substance is preferably sodium hydroxide.
6. it is characterized in that in accordance with the method for claim 1: in catalyzer used, contain the active component A with shortening function and the tungstenic active ingredient B with catalyse cellulose degradation function; Active component A comprises one or more metal or the metal oxide in cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum; The active ingredient B of tungstenic comprises the various compounds of tungsten simple substance and tungsten, i.e. one or more in the oxyhydroxide of the muriate of the sulfide of the oxide compound of the carbide of tungsten, tungsten, tungsten nitride, tungsten phosphide, tungsten, tungsten, tungsten, tungsten, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxotungstate, heteropoly tungstic acid.
7. in accordance with the method for claim 6, it is characterized in that: described catalyst activity component A and active ingredient B can be supported on porous support jointly, also can be supported on individually separately and on porous support, form composite catalyst, described carrier is one or two or more kinds complex carrier of gac, aluminum oxide, silicon oxide, silicon carbide, zirconium white, zinc oxide, titanium dioxide; The content of activity component metal on catalyzer is at 0.05-60 wt%;
Or described catalyst activity component A also can be with unsupported form Individual existence; Or described catalyst activity B component also can be with unsupported form Individual existence;
In use, the metal active composition of catalyst A and the activeconstituents weight ratio of catalyst B are between 0.1-10 times of scope, and wherein the weight of B activeconstituents is with tungsten weighing scale.
8. in accordance with the method for claim 1, it is characterized in that: range of reaction temperature is at 150-350 DEG C, the pressure 3-10 MPa of hydrogen in reaction process, reaction times is 30 min – 3 h, the mass ratio of reaction raw materials and catalyzer is 1:1-30000:1, and wherein the quality of catalyzer is with active metal weighing scale.
9. in accordance with the method for claim 8, it is characterized in that: reaction raw materials is 3:1-3000:1 with the quality of catalyzer than scope, and wherein the quality of catalyzer is with active metal weighing scale.
10. in accordance with the method for claim 8, it is characterized in that: temperature of reaction is 220-280 DEG C, reaction raw materials is 4:1-1000:1 with the quality of catalyzer than scope, and wherein the quality of catalyzer is with active metal weighing scale.
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| WO2016114660A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate source |
| WO2016114659A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate source |
| WO2016114661A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Continuous process for preparing ethylene glycol from a carbohydrate source |
| NL2014120A (en) * | 2015-01-13 | 2016-09-26 | Avantium Knowledge Centre Bv | Process for preparing ethylene glycol from a carbohydrate. |
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| WO2016114658A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016114660A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate source |
| WO2016114659A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate source |
| WO2016114661A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Continuous process for preparing ethylene glycol from a carbohydrate source |
| NL2014120A (en) * | 2015-01-13 | 2016-09-26 | Avantium Knowledge Centre Bv | Process for preparing ethylene glycol from a carbohydrate. |
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