CN102731255A - 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 for preparing terepthaloyl moietie, specifically is the method for feedstock production terepthaloyl moietie by corn cob.
Background technology
Terepthaloyl moietie is important large Essential Chemistry article, and global terepthaloyl moietie output reached more than 2,000 ten thousand tons in 2010, and wherein, 80% is used for the PET resin synthesizes, and 12% is used for deicing fluid synthesizes, and about 8% is used for other chemical intermediates.The existing industrial product route of terepthaloyl moietie mainly is to depend on oil ethene resource.Utilizing reproducible biomass resource synthesizing glycol technology is to realize one of important channel [the document 1:Process for the preparation of lower polyhydric alcohols of fossil energy substitution of resources; Patent; No.US5107018. document 2:Preparation of lower polyhydric alcohols; Patent; No.US5210335. document 3: a kind of novel process of producing terepthaloyl moietie, CN200610068869.5. document 4: a kind of method of producing divalent alcohol and polyvalent alcohol by cracking sorbierite, CN200510008652.0].
2008; The scientific research personnel of the Dalian Chemistry and Physics Institute discovers first; Mierocrystalline cellulose can directly be obtained terepthaloyl moietie [document 5:Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts by the 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.].Adopted purified Microcrystalline Cellulose in the research, the yield of terepthaloyl moietie reaches 60-75%.Yet the Mierocrystalline cellulose of occurring in nature always is present in the plant materials, forms with complicacies such as semicellulose, xylogen and is woven together.Therefore, utilize the full biomass Mierocrystalline cellulose directly to transform preparing ethylene glycol, can be in the influence that receives these components in varying degrees.Discover; Be that raw material is when carrying out catalyzed conversion with the corn straw; The yield of terepthaloyl moietie and the preprocessing process of raw material have very big relation [document 8:Catalytic Hydrogenation of Corn Stalk to Ethylene Glycol and 1,2-Propylene Glycol, Ind.Eng.Chem.Res.2011; 50,6601-6608].Have nothing in common with each other because different weave constructions that plant material had and composition constitute, therefore, need develop full biomass cellulosic material pretreatment process and catalytic reaction process pointedly, to obtain best terepthaloyl moietie yield.
Contain abundant semicellulose, Mierocrystalline cellulose and a certain amount of xylogen in the corn cob.The semicellulose that is contained can pass through certain method and extract chemical and healthcare products such as production such as the process that is used for biological fermentation, catalyzed conversion butanols, furfural, xylooligosaccharides, Xylitol.And the raw material of remaining rich cellulose then can be used for catalyzed conversion to produce terepthaloyl moietie.Thereby the corn cob base preparation of cellulose terepthaloyl moietie of development simple and effective has important use and is worth.
Summary of the invention
The invention provides a kind of method by corn cob catalyzed conversion preparing ethylene glycol.
Behind corn cob raw material process water vapor explosion treatment or the dilute acid hydrolysis, corn cob is used the strong alkaline aqueous solution immersion treatment, passes through the clear water rinsing again to neutral, places under the catalytic hydrogenation reaction condition to prepare terepthaloyl moietie.
Corn cob water vapor explosion treatment process is for to place autoclave with corn cob; In autoclave, feed high-temperature high-pressure steam, pressure is 0.5-2.0MPa, and pressure hold time is 0.5-20min; Temperature is 160-220 ℃, and the pressure that discharges autoclave suddenly then is to normal pressure.
The water cut of corn cob is at 25-60%, is 5-60%v/v in the charge of steam explosion reaction kettle, and the pressure that discharges autoclave suddenly is meant and makes the autoclave internal pressure reduce to normal pressure within 0.001 second to 5 seconds.
Corn cob is used dilute acid hydrolysis; Temperature is-180 ℃ of normal temperature (0-30 ℃); The 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, the formic acid, and the time is 5min-24h, and the mass ratio of corn cob raw material and acid solution is 1: 1-1: 100.When hydrolysis temperature was higher than 100 ℃, preprocessing process carried out in airtight still, and pressure is pairing autogenous pressure under 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; 10-80 ℃ is soaked 30min-48h down.
The alkali metal hydroxide that contains mass concentration 0.3-5wt% in the strong alkaline aqueous solution, the mass ratio of raw material and alkaline solution is 1: 10, strong alkaline substance is preferably sodium hydroxide; 20-50 ℃ is soaked 1-24h down.
The catalytic hydrogenation reaction process is carried out under the agitation condition in closed pressure vessel; Temperature of reaction >=150 ℃; Hydrogen pressure 0.1-15MPa in the reaction process, the mass content of reactant in the aqueous solution is 1-30wt%, the reaction times is no less than 5min; Contain active component A with shortening function and the tungstenic active ingredient B with catalyse cellulose degradation function in the used catalyzer, consumption is a catalytic amount; In use, the activeconstituents of the metal active composition of catalyst A and catalyst B (in tungsten weight) weight ratio is between 0.02-3000 times of scope.
Contain active component A with shortening function and tungstenic active ingredient B in the used catalyzer with catalyse cellulose degradation function; Active component A comprises one or more metal or the MOX in cobalt, nickel, ruthenium, rhodium, palladium, iridium, the platinum; The active ingredient B of tungstenic comprises all cpds of tungsten simple substance and tungsten, 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 wolfram varbide, tungsten nitride, tungsten phosphide, the tungsten of tungsten, tungsten one or more specifically.
Said catalyst activity component A and active ingredient B can be supported on the porous support jointly; Also can be supported on individually separately and constitute composite catalyst on the porous support, 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 0.05-60wt%;
Perhaps, said catalyst activity component A also can be with unsupported form exist singly; Perhaps, said catalyst activity B component also can be with unsupported form exist singly;
In use, the activeconstituents of the metal active composition of catalyst A and catalyst B (in tungsten weight) weight ratio is between 0.1-10 times of scope.
Range of reaction temperature is at 150-350 ℃; Preferred temperature of reaction is 220-280 ℃; The pressure 3-10MPa of preferred hydrogen in the reaction process, the preferred reaction time is 30min-3h, the quality of reaction raw materials and catalyzer (in the reactive metal quality) is than being 1: 1-30000: 1.The quality of reaction raw materials and catalyzer (in the reactive metal quality) is 3 than preferable range: 1-3000: 1, and preferred scope is 4: 1-1000: 1.
The catalytic hydrogenation reaction device adopts closed pressure vessel, comprises batch reactor formula reactor drum, semibatch reaction tank reactor, slurry attitude hearth reactor, circulating fluid bed type reactor drum.
The effect that the present invention is useful
With the corn cob is raw material, combines catalytic reaction process through simple and easy to do pretreatment mode, has realized that corn cob sill matter cellulosic material is converted into terepthaloyl moietie with high yield.
Embodiment
Embodiment 1
Get corn cob powder (20-40 order) 10kg, adding water, to make its water cut be 30wt%, places 160 ℃ of steam explosion reactor drums, in 60 seconds of (pressure 1.0MPa) constant voltage, carries out the steam explosion operation then.To the 8kg solid residue (dry weight) that obtains, add the NaOH aqueous solution of 50kg concentration 1wt% to it, room temperature is soaked 12h down for 25 ℃, and the clear water rinsing obtains 6kg (dry weight) cellulosic material to neutral then.
Embodiment 2
Get corn cob powder (10-20 order) 10kg, adding water, to make its water cut be 45wt%, places 30 seconds of 180 ℃ of steam explosion reactor drums (pressure 1.2MPa) constant voltage, carries out the steam explosion operation then.To the 7.5kg solid residue (dry weight) that obtains, add the NaOH aqueous solution of 15kg concentration 5wt% to it, room temperature is soaked 6h down for 20 ℃, and the clear water rinsing obtains 5.8kg (dry weight) cellulosic material to neutral then.
Embodiment 3
Get corn cob powder (40-60 order) 10kg, adding the 50kg volumetric molar concentration is the diluted hydrochloric acid aqueous solution of 0.03mol/L, airtightly is heated to 140 ℃ of hydrolysis 6 hours.Then; Centrifuging goes out solid insoluble, under room temperature, soaks 12 hours according to solid and 1: 10 weight ratio of solution with the sodium hydroxide solution of concentration 2wt%, then the spinning solid insoluble; To neutral, obtain 5.0kg (dry weight) cellulosic material with the clear water rinsing.
Embodiment 4
Get corn cob powder (40-60 order) 10kg, adding the 50kg volumetric molar concentration is the diluted hydrochloric acid aqueous solution of 0.3mol/L, airtightly is heated to 80 ℃ of hydrolysis 2 hours.Then; Centrifuging goes out solid insoluble, under room temperature, soaks 12 hours according to solid and 1: 1 weight ratio of solution with the sodium hydroxide solution of 10wt%, then the spinning solid insoluble; To neutral, obtain 4.8kg (dry weight) cellulosic material with the clear water rinsing.
Embodiment 5
Get the Mierocrystalline cellulose sample that 5.0g handles well according to embodiment 1,2 respectively, add 100ml water, the 0.1g wolframic acid, 5%Ru/AC catalyzer 0.1g, 250 ℃ are reacted 2h in autoclave, charge into 5Mpa hydrogen before the reaction, 500 rev/mins of stirring velocitys.After reaction finishes, reduce to room temperature, still and the centrifugal liquid product that obtains are opened in pressure release, product with chromatograph-mass spectrometer accurately qualitative after, with liquid-phase chromatographic analysis polyvalent alcohol product yield.
Embodiment 6
Get the Mierocrystalline cellulose sample that 5.0g handles well according to embodiment 3,4 respectively, add 100ml water, 0.25g 5%Ni-30%W
2The C/AC tungsten carbide catalyst, 240 ℃ are reacted 1h in autoclave, charge into 5Mpa hydrogen before the reaction, 500 rev/mins of stirring velocitys.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
The comparative example 1
Get 10kg corn cob powder (20-40 order); Adding water, to make its water cut be 30wt%; Place 60 seconds of 160 ℃ of steam explosion reactor drums (pressure 1.0MPa) constant voltage; After carrying out steam explosion operation then and carrying out the water vapor explosion treatment, the clear water rinsing obtains 8kg (dry weight) cellulose solids residuum to neutral then.
Get the Mierocrystalline cellulose sample that 5.0g handles well, add 100ml water, the 0.1g wolframic acid, 5%Ru/AC catalyzer 0.1g, with in the autoclave 250 ℃ react 2h, charge into 5Mpa hydrogen before the reaction, 500 rev/mins of stirring velocitys.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
The comparative example 2
Get 7kg corn cob powder (20-40 order), add the NaOH aqueous solution of 50kg concentration 1wt% to it, room temperature is soaked 12h down for 25 ℃, and the clear water rinsing obtains 6kg (dry weight) cellulose solids residuum to neutral then.
Get the Mierocrystalline cellulose sample that 5.0g handles well, add 100ml water, the 0.1g wolframic acid, 5%Ru/AC catalyzer 0.1g, with in the autoclave 250 ℃ react 2h, charge into 5Mpa hydrogen before the reaction, 500 rev/mins of stirring velocitys.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
The comparative example 3
Get corn cob powder (40-60 order) 10kg, adding the 50kg volumetric molar concentration is the diluted hydrochloric acid aqueous solution of 0.03mol/L, airtightly is heated to 140 ℃ of hydrolysis 6 hours.Centrifuging goes out solid insoluble then, to neutral, obtains cellulosic material with the clear water rinsing.
Get 5.0g Mierocrystalline cellulose sample, add 100ml water, 0.25g 5%Ni-30%W2C/AC tungsten carbide catalyst, 240 ℃ are reacted 1h in autoclave, charge into 5Mpa hydrogen before the reaction, 500 rev/mins of stirring velocitys.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
The comparative example 4
Get the undressed corn cob powder of 5.0g (20-40 order), add 100ml water, the 0.1g wolframic acid, 5%Ru/AC catalyzer 0.1g, with in the autoclave 250 ℃ react 2h, charge into 5Mpa hydrogen before the reaction, 500 rev/mins of stirring velocitys.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, liquid-phase chromatographic analysis polyvalent alcohol product yield are opened in pressure release.
The comparative example 5
Change corn cob into corn straw, combine dilute alkaline soln to carry out pre-treatment, obtain cellulosic material according to embodiment 1 identical condition water vapour explosion.Afterwards, carry out catalytic conversion reaction with the cellulosic material of gained according to the condition of embodiment 5, with liquid-phase chromatographic analysis polyvalent alcohol product yield.
The comparative example 6
Change corn cob into broomcorn straw, combine dilute alkaline soln to carry out pre-treatment, obtain cellulosic material according to embodiment 3 identical condition water vapour explosions.Afterwards, carry out catalytic conversion reaction with the cellulosic material of gained according to the condition of embodiment 6, with liquid-phase chromatographic analysis polyvalent alcohol product yield.
Embodiment 7
Under embodiment 5,6 and comparative example's 1,2,3,4 conditions, the cellulosic material catalyzed conversion is comparative result as a result.Shown in table.
The reaction result that the corn cob catalytic material that table one, various condition are handled transforms preparing ethylene glycol compares
Listed result can see from above form; The steam explosion combined alkali is handled; And diluted acid combined alkali cellulose processed biomass material, catalyzed conversion is a terepthaloyl moietie with high yield, reaches 65%; Be significantly higher than that simple steam explosion is handled 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
Among the embodiment 5,6 among cellulosic catalyzed conversion result of corn cob and the comparative example 5,6 the catalyzed conversion result of corn straw and sorghum stalk relatively, shown in table two.
The reaction result of table two, different cellulosic material catalyzed conversion preparing ethylene glycols relatively
Can see that by the contrast of the result in the form this reaction process has good selectivity and yield to the conversion preparing ethylene glycol of corn cob.And for other biological raw material corn straw and sorghum stalk, because raw material mix and composition and corn cob is different, even through behind the identical preprocessing process, the catalytic effect in reaction does not have the ideal of corn cob raw material.
Claims (10)
1. one kind is the method for feedstock production terepthaloyl moietie with the corn cob; It is characterized in that: behind corn cob raw material process water vapor explosion treatment or the dilute acid hydrolysis; Corn cob is used the strong alkaline aqueous solution immersion treatment, passes through the clear water rinsing again to neutral, places under the catalytic hydrogenation reaction condition to prepare terepthaloyl moietie;
The catalytic hydrogenation reaction process is carried out under the agitation condition in closed pressure vessel; Temperature of reaction >=150 ℃; Hydrogen pressure 0.1-15MPa in the reaction process, the mass content of reactant in the aqueous solution is 1-30wt%, the reaction times is no less than 5min; Contain active component A with shortening function and the tungstenic active ingredient B with catalyse cellulose degradation function in the used catalyzer, consumption is a catalytic amount; In use, the activeconstituents of the metal active composition of catalyst A and catalyst B (in tungsten weight) weight ratio is between 0.02-3000 times of scope.
2. according to the described method of claim 1; It is characterized in that: corn cob water vapor explosion treatment process is for to place autoclave with corn cob; In autoclave, feed high-temperature high-pressure steam, pressure is 0.5-2.0MPa, and pressure hold time is 0.5-20min; Temperature is 160-220 ℃, and the pressure that discharges autoclave suddenly then is to normal pressure.
3. according to the described method of claim 2; It is characterized in that: the water cut of corn cob is at 25-60%; Charge in the steam explosion reaction kettle is 5-60%v/v, and the pressure that discharges autoclave suddenly is meant and makes the autoclave internal pressure reduce to normal pressure within 0.001 second to 5 seconds.
4. according to the described method of claim 1; It is characterized in that: corn cob is used dilute acid hydrolysis; Temperature is a normal temperature-180 ℃, and the diluted acid volumetric molar concentration is 0.02-0.6mol/L, and acid comprises one or more in hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, acetic acid, the formic acid; Time is 5min-24h, and the mass ratio of corn cob raw material and acid solution is 1: 1-1: 100.
5. according to the described method of claim 1, it is characterized in that: 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; 10-80 ℃ is soaked 30min-48h down.
6. according to the described method of claim 1, it is characterized in that: contain the alkali metal hydroxide of mass concentration 0.3-5wt% in the strong alkaline aqueous solution, the mass ratio of raw material and alkaline solution is 1: 10, and strong alkaline substance is preferably sodium hydroxide; 20-50 ℃ is soaked 1-24h down.
7. according to the described method of claim 1, it is characterized in that: contain active component A with shortening function and tungstenic active ingredient B in the used catalyzer with catalyse cellulose degradation function; Active component A comprises one or more metal or the MOX in cobalt, nickel, ruthenium, rhodium, palladium, iridium, the platinum; The active ingredient B of tungstenic comprises all cpds of tungsten simple substance and tungsten, 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 wolfram varbide, tungsten nitride, tungsten phosphide, the tungsten of tungsten, tungsten one or more specifically.
8. according to the described method of claim 7; It is characterized in that: said catalyst activity component A and active ingredient B can be supported on the porous support jointly; Also can be supported on individually separately and constitute composite catalyst on the porous support, 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 0.05-60wt%;
Perhaps, said catalyst activity component A also can be with unsupported form exist singly; Perhaps, said catalyst activity B component also can be with unsupported form exist singly;
In use, the activeconstituents of the metal active composition of catalyst A and catalyst B (in tungsten weight) weight ratio is between 0.1-10 times of scope.
9. according to the described method of claim 1; It is characterized in that: range of reaction temperature is at 150-350 ℃; Preferred temperature of reaction is 220-280 ℃; The pressure 3-10MPa of preferred hydrogen in the reaction process, the preferred reaction time is 30min-3h, the mass ratio of reaction raw materials and catalyzer (in the reactive metal quality) is 1: 1-30000: 1.
10. according to the described method of claim 9, it is characterized in that: the quality of reaction raw materials and catalyzer (in the reactive metal quality) is 3 than preferable range: 1-3000: 1, and preferred scope is 4: 1-1000: 1.
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| CN112961046A (en) * | 2021-02-06 | 2021-06-15 | 中国石油大学(华东) | Method for alkali-free synthesis of glycolic acid by using waste biomass |
| CN112961046B (en) * | 2021-02-06 | 2022-10-14 | 中国石油大学(华东) | Method for alkali-free synthesis of glycolic acid by using waste biomass |
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