CN102731253A - Method capable of inhibiting generation of cyclic ether alcohol and used for preparing glycol by catalytic conversion of cellulose - Google Patents
Method capable of inhibiting generation of cyclic ether alcohol and used for preparing glycol by catalytic conversion of cellulose Download PDFInfo
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Abstract
The invention provides a method capable of inhibiting generation of cyclic ether alcohol and used for preparing glycol by catalytic conversion of cellulose, characterized by conducting catalytic hydrogenation in an enclosed high pressure container with stirring at the reaction temperature of no less than 150 DEG C under the hydrogen pressure of 0.1-15 MPa, wherein the mass content of the reactant in the aqueous solution is 1-30 wt%, and the reaction time is no less than 5 min; the catalyst comprises an active ingredient A with the function of catalytic hydrogenation, a tungsten-containing active ingredient B with the function of catalyzing cellulose degradation, and a catalytic active ingredient C containing rhenium. According to the invention, cyclic ether alcohol by-product in the reaction products with the boiling point close to that of glycol is significantly reduced, thus impurities in subsequent distillation separation product of the glycol product are reduced, and the product purity of the glycol product is raised.
Description
Technical field
The present invention relates to a kind of method for preparing terepthaloyl moietie, specifically a kind of method that suppresses the Mierocrystalline cellulose catalyzed conversion preparing ethylene glycol of cyclic ethers alcohol generation.
Background technology
Terepthaloyl moietie is important basic energy resource chemical, and the consumption of whole world terepthaloyl moietie in 2010 is mainly used in synthesising fibre polyester, unsaturated polyester, automobile antifreeze solution and chemical midbody near 2,000 ten thousand tons.At present; The production of terepthaloyl moietie mainly depends on oil ethene resource [document 1: Cui Xiaoming; Domestic and international terepthaloyl moietie production development overview, chemical industry, 2007; 25; (4), 15-21. document 2:Process for preparing ethanediol by catalyzing epoxyethane hydration, Patent No.CN1463960-
CN1204103-C].Utilizing reproducible biomass resource synthesizing glycol technology is to realize one of important channel [the document 3:Process for the preparation of lower polyhydric alcohols of fossil energy substitution of resources; Patent; No.US5107018. document 4:Preparation of lower polyhydrical cohols; Patent; No.US5210335. document 3: a kind of novel process of producing terepthaloyl moietie, CN200610068869.5. document 5: a kind of method of producing divalent alcohol and polyvalent alcohol by cracking sorbierite, CN200510008652.0].
Mierocrystalline cellulose is the maximum biomass resource of the ubiquitous output of occurring in nature.And, there are abundant carbon, hydrogen, Sauerstoffatom in the cellulosic molecule structure, elementary composition very similar with in the glycol molecule.Thereby, be that the reaction that reaction raw materials prepares terepthaloyl moietie has very high Atom economy with the Mierocrystalline cellulose, be highly desirable cellulose resource is utilized route.
2008; The scientific research personnel of the Dalian Chemistry and Physics Institute discovers first; Mierocrystalline cellulose can directly be obtained terepthaloyl moietie [document 6:Direct catalyticconversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts by the catalyzed conversion highly selective on tungsten-based catalyst; Angew.Chem.Int.Ed.2008,47,8510-8513.Document 7:transition meta-tungsten bimetallic catalysts for the conversion of cellulose into ethylene glycol, ChemSusChem 2010,3,63-66.Document 8:A new 3D me s oporous carbon replicated from commercial silica as a catalyst support for direct conversion of cellulose into ethylene glycol; Chem.Commun.; 2010,46,862864.].Mierocrystalline cellulose transforms fully in the reaction, and the yield of terepthaloyl moietie is up to 60-75%.
On the other hand; Further find in the research, in the preparing ethylene glycol from cellulose process, except obtaining terepthaloyl moietie, Ucar 35, butyleneglycol product; Also exist some to have the alcohol of cyclic ether structure; Comprise tetrahydrofurfuryl alcohol (boiling point 178C), 3-hydroxyl tetrahydrofuran (boiling point 181C) and 2-methylol tetrahydropyrans (boiling point 187C).The boiling point and the terepthaloyl moietie boiling point 197.8C of these cyclic ethers alcohol are more approaching, are difficult to effectively from the terepthaloyl moietie product rectifying separation and remove.And being used for the polyester building-up process at terepthaloyl moietie, these products produce adverse influence.
Therefore, how can in reaction, guarantee the high yield while of terepthaloyl moietie, the generation that reduces or eliminates undesirable cyclic ethers alcohol by product is one has problem to be solved.
Summary of the invention
The present invention provides a kind of method that can suppress the Mierocrystalline cellulose catalyzed conversion preparing ethylene glycol of cyclic ethers alcohol generation.
Cellulosic 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 the active component A with shortening function, the tungstenic active ingredient B with catalyse cellulose degradation function and rhenium-containing catalytic active component C in the used catalyzer, consumption is a catalytic amount; In use, the metal active composition of catalyst A and the activeconstituents of catalyst B (in tungsten weight) weight ratio are between 0.02-3000 times of scope, and preferable range is between 0.05-100 times; The metal active composition of catalyst A and the activeconstituents of catalyzer C (in rhenium metal weight) weight ratio are between 0.02-3000 times of scope, and preferable range is between 0.1-100 times.
Contain the active component A with shortening function, tungstenic active ingredient B and rhenium-containing catalytic active component C 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 tungsten, wolfram varbide, tungsten nitride, tungsten phosphide, tungsten one or more specifically; Rhenium-containing catalytic active component C comprises rhenium metal, rhenium+1 ,+2 ,+3 ,+4 ,+5 ,+6 ,+7 valence state oxide compound (as: rhenium heptoxide Re
2O
7, rhenium dioxide ReO
2, rhenium trioxide ReO
3, rhenium sesquioxide Re
2O
3With oxidation two rhenium Re
2O etc.) one or both in.
Temperature of reaction >=150 ℃, TR is at 150-350 ℃; Preferred temperature of reaction is 220-280 ℃, the pressure 3-10MPa of preferred hydrogen in the reaction process, and the preferred reaction time is 30min 3h.
Said catalyst activity component A and active ingredient B, active ingredient C can three kinds be supported on the porous support jointly; Also can be supported on the porous support jointly by any two kinds of independent assortments; Can also 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 0.05-50wt%;
Said catalyst activity component A, B, C also can be with unsupported form exist singlys;
The mass ratio of reaction raw materials and catalyzer (in the reactive metal quality) is 1: 1-30000: 1, and preferable range is 3: 1-3000: 1, preferred scope is 4: 1-1000: 1.
Described fibrin reaction raw material sources comprise corn cob in plant, or stalk, and stalk derives from corn, wheat, cotton, Chinese sorghum, soybean, paddy rice, sugarcane, perhaps derive from urban domestic wastewater, timber, forestry waste, recovery paper product.
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:
Method provided by the invention not only can keep the high yield of Mierocrystalline cellulose catalyzed conversion preparing ethylene glycol, simultaneously, reduces and eliminated the generation of cyclic ethers alcohol sub product, has reduced the rectifying separation difficulty of terepthaloyl moietie product, has improved rectifying terepthaloyl moietie product gas purity.
Embodiment
Embodiment 1
Get corn straw 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 ℃, leaches the back to wherein adding the ydrogen peroxide 50 that 50kg concentration is 1wt%, soaks 12h under the room temperature; The clear water rinsing obtains 5kg (dry weight) corn straw cellulosic material to neutral then.
The corn straw powder is replaced with broomcorn straw,, can obtain corresponding cellulosic material according to top the same method.
Embodiment 2
Get 10.0g corn straw Mierocrystalline cellulose (gained among the embodiment 1) and add 100ml water; 0.1g wolframic acid; 0.1g 5%Ru/AC catalyzer; 0.05g 0.5%Ir-1%ReOx/AC (0＜x≤3.5) in autoclave 250 ℃ react 2h, 500 rev/mins of stirring velocitys, hydrogen pressure 7MPa in the reaction process.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, gas chromatographic analysis polyvalent alcohol product and cycloalcohol by product yield are opened in pressure release.
The comparative example 1
Get 10.0g corn straw Mierocrystalline cellulose (gained among the embodiment 1), add 100ml water, the 0.1g wolframic acid; 0.1g 5%Ru/AC catalyzer; 0.05g 0.5%Ir/AC in autoclave 250 ℃ react 2h, 500 rev/mins of stirring velocitys, hydrogen pressure 7MPa in the reaction process.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.
Embodiment 3
Get 10.0g broomcorn straw Mierocrystalline cellulose (gained among the embodiment 1) and add 100ml water, 0.1g ammonium metawolframate, 0.1g Raney's nickel catalyst, 0.05g 2%Ru-0.2%Re/SiO
2240 ℃ are reacted 2h in autoclave, 500 rev/mins of stirring velocitys, hydrogen pressure 7MPa in the reaction process.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, gas chromatographic analysis polyvalent alcohol product and cycloalcohol by product yield are opened in pressure release.
The comparative example 2
Get 10.0g broomcorn straw Mierocrystalline cellulose (gained among the embodiment 1) and add 100ml water, 0.1g ammonium metawolframate, 0.1g Raney's nickel catalyst, 0.05g 2%Ru/SiO
2250 ℃ are reacted 2h in autoclave, 500 rev/mins of stirring velocitys, hydrogen pressure 7MPa in the reaction process.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, gas chromatographic analysis polyvalent alcohol product and cycloalcohol by product yield are opened in pressure release.
Embodiment 4
Get the 10.0g Microcrystalline Cellulose and add 100ml water, 0.5g 30%W
2C/AC, 0.1g 1%Rh/AC, 0.05g ReO
2240 ℃ are reacted 2h in autoclave, 500 rev/mins of stirring velocitys, hydrogen pressure 7MPa in the reaction process.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, gas chromatographic analysis polyvalent alcohol product and cycloalcohol by product yield are opened in pressure release.
The comparative example 3
Get the 10.0g Microcrystalline Cellulose and add 100ml water, 0.5g 30%W
2C/AC, 0.05g MoO
3240 ℃ are reacted 2h in autoclave, 500 rev/mins of stirring velocitys, hydrogen pressure 7MPa in the reaction process.Reaction is reduced to room temperature after finishing, and still and the centrifugal liquid product that obtains, gas chromatographic analysis polyvalent alcohol product and cycloalcohol by product yield are opened in pressure release.
Embodiment 5
Under the differential responses condition, the product of cellulose conversion preparing ethylene glycol is formed and the yield situation compares.Shown in table.
The reaction result of cellulose conversion preparing ethylene glycol relatively under table one, the different catalysts condition
Listed result can see from above form; When being used for the cellulose conversion catalyst for reaction and containing tungsten active ingredient, rhenium active ingredient and hydrogenation activity component simultaneously; The cyclic ethers alcohol by product that reaction process produced significantly is less than and does not contain three kinds of active constituent catalyst reaction products resulting simultaneously, embodies significant technical progress.
Embodiment 6
The rectifying of terepthaloyl moietie product.The product liquid 1L that the extracting cellulose preparing ethylene glycol obtains carries out rectification under vacuum in rectifier unit, vacuum tightness is 0.1bar, and the theoretical plate number of rectifying volumn is 10, and reflux ratio is 5.Collect the product of temperature range 120-125C, use the gas chromatographic analysis product purity.Products obtained therefrom purity is shown in table two.
Cellulose conversion preparing ethylene glycol product rectifying cut purity relatively under table two, the different catalysts condition
Can see that from table two the terepthaloyl moietie product that obtains in the method for the invention is through after the rectifying, the content of cyclic ethers alcohol significantly is lower than comparative example's result in the product, embodies significant technical progress.In the method provided by the invention, adopt the ternary component catalyzer, when one-step catalytic transforms preparing ethylene glycol from cellulose, significantly reduce or elimination cyclic ethers alcohol by product,, improve the quality of terepthaloyl moietie product so that reduce the difficulty of terepthaloyl moietie rectification and purification.
Claims (7)
1. one kind is suppressed the method that the pure Mierocrystalline cellulose catalyzed conversion that generates of cyclic ethers prepares terepthaloyl moietie; It is characterized in that: 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 the active component A with shortening function, the tungstenic active ingredient B with catalyse cellulose degradation function and rhenium-containing catalytic active component C 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; The metal active composition of catalyst A and the activeconstituents of catalyzer C (in rhenium metal weight) weight ratio are between 0.02-3000 times of scope.
2. according to the described method of claim 1, it is characterized in that: contain the active component A with shortening function, tungstenic active ingredient B and rhenium-containing catalytic active component C 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 tungsten, wolfram varbide, tungsten nitride, tungsten phosphide, tungsten one or more specifically; Rhenium-containing catalytic active component C comprise rhenium metal, rhenium+1 ,+2 ,+3 ,+4 ,+5 ,+6 ,+in the 7 valence state oxide compounds one or both;
Said catalyst activity component A and active ingredient B, active ingredient C can three kinds be supported on the porous support jointly; Also can be supported on the porous support jointly by any two kinds of independent assortments; Can also 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%;
Said catalyst activity component A, B, C also can be with unsupported form exist singlys.
3. according to the described method of claim 1, it is characterized in that: the metal active composition of catalyst A and the activeconstituents of catalyst B (in tungsten weight) weight ratio preferable range are between 0.05-100 times.
4. according to the described method of claim 1, it is characterized in that: the metal active composition of catalyst A and the activeconstituents of catalyzer C (in rhenium metal weight) weight ratio preferable range are between 0.1-100 times of scope.
5. 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.
6. according to the described method of claim 5, 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.
7. according to the described method of claim 1; It is characterized in that: described fibrin reaction raw material sources are in plant; Comprise corn cob; Or stalk, stalk derives from corn, wheat, cotton, Chinese sorghum, soybean, paddy rice, sugarcane, perhaps derives from urban domestic wastewater, timber, forestry waste, recovery paper product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107406358A (en) * | 2015-01-13 | 2017-11-28 | 阿凡田知识中心有限公司 | The continuous processing of ethylene glycol is prepared from carbohydrate |
| CN107406359A (en) * | 2015-01-13 | 2017-11-28 | 阿凡田知识中心有限公司 | The technique for preparing ethylene glycol from carbohydrate |
Citations (1)
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| CN101443300A (en) * | 2006-05-08 | 2009-05-27 | 维仁特能源系统公司 | Methods and systems for generating polyols |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101443300A (en) * | 2006-05-08 | 2009-05-27 | 维仁特能源系统公司 | Methods and systems for generating polyols |
Non-Patent Citations (2)
| Title |
|---|
| MING-YUAN ZHENG ET AL.: "Transition Metal-Tungsten Bimetallic Catalysts for the Conversion of Cellulose into Ethylene Glycol", 《CHEMSUSCHEM》, vol. 3, no. 1, 25 January 2010 (2010-01-25), pages 63 - 66 * |
| 赵凤阁: "乙二醇制备方法的专利技术进展及评述", 《精细与专用化学品》, vol. 19, no. 7, July 2011 (2011-07-01), pages 38 - 41 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107406358A (en) * | 2015-01-13 | 2017-11-28 | 阿凡田知识中心有限公司 | The continuous processing of ethylene glycol is prepared from carbohydrate |
| CN107406359A (en) * | 2015-01-13 | 2017-11-28 | 阿凡田知识中心有限公司 | The technique for preparing ethylene glycol from carbohydrate |
| US10294180B2 (en) | 2015-01-13 | 2019-05-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate source |
| EP3245180B1 (en) * | 2015-01-13 | 2020-04-08 | Avantium Knowledge Centre B.v. | Process for preparing ethylene glycol from a carbohydrate source |
| CN107406358B (en) * | 2015-01-13 | 2020-12-08 | 阿凡田知识中心有限公司 | Continuous process for the preparation of ethylene glycol from a carbohydrate source |
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