CN102731253B - 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 of preparing ethylene glycol, specifically a kind of method that suppresses the Mierocrystalline cellulose catalyzed conversion preparing ethylene glycol of cyclic ethers alcohol generation.
Background technology
Ethylene glycol is important basic energy resource chemical, and the consumption of whole world ethylene glycol in 2010 approaches 2,000 ten thousand tons, is mainly used in synthesising fibre polyester, unsaturated polyester, automobile antifreeze solution and chemical intermediate.At present, the production of ethylene glycol mainly depends on oil ethene resource [document 1: Cui little Ming, Ethylene Glycol 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 one of important channel of realizing fossil energy substitution of resources [document 3:Process for the preparation of lower polyhydric alcohols, patent, No.US5107018. document 4:Preparation of lower polyhydrical cohols, patent, No.US5210335. document 3: a kind of novel process of producing ethylene glycol, CN200610068869.5. document 5: a kind of method of being produced dibasic 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, in cellulosic molecule structure, there is abundant carbon, hydrogen, Sauerstoffatom, elementary composition very similar with glycol molecule.Thereby the reaction that the Mierocrystalline cellulose of take is prepared ethylene glycol as reaction raw materials has very high Atom economy, be that highly desirable cellulose resource is utilized route.
2008, the scientific research personnel of the Dalian Chemistry and Physics Institute studies discovery first, Mierocrystalline cellulose can obtain ethylene glycol [document 6:Direct catalyticconversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts by direct 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.].In reaction, Mierocrystalline cellulose transforms completely, and the yield of ethylene glycol is up to 60-75%.
On the other hand, further in research, find, in preparing ethylene glycol from cellulose process, except obtaining ethylene glycol, propylene glycol, butyleneglycol product, also exist some with 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 of these cyclic ethers alcohol and ethylene glycol boiling point 197.8C are more approaching, are difficult to effectively rectifying separation from ethylene glycol product and remove.And these products produce adverse influence at ethylene glycol for process of polyester synthesizing.
Therefore, how can in reaction, guarantee the high yield of ethylene glycol simultaneously, the generation that reduces or eliminates undesirable cyclic ethers alcohol by product is one problem to be solved.
Summary of the invention
The 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 agitation condition in closed pressure vessel, temperature of reaction >=150 ℃, 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 and have the active component A of shortening function, the tungstenic active ingredient B with catalyse cellulose degradation function and rhenium-containing catalytic active component C, 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, and preferable range is between 0.05-100 times; The metal active composition of catalyst A and the activeconstituents of catalyzer C (with rhenium metal weighing scale) weight ratio are between 0.02-3000 times of scope, and preferable range is between 0.1-100 times.
In catalyzer used, contain and there is the active component A of shortening function, the tungstenic active ingredient B with catalyse cellulose degradation function and rhenium-containing catalytic active component C; 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, comprise specifically the oxide compound of tungsten, wolfram varbide, tungsten nitride, tungsten phosphide, tungsten, the muriate of the sulfide of tungsten, tungsten, one or more in the oxyhydroxide of tungsten, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxotungstate, heteropoly tungstic acid; 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 ℃, temperature range is at 150-350 ℃; Preferred temperature of reaction is 220-280 ℃, the pressure 3-10MPa of preferred hydrogen in reaction process, and the preferred reaction time is 30min 3h.
Described catalyst activity component A and active ingredient B, active ingredient C can three kinds be supported on porous support jointly, also can jointly be supported on porous support by any two kinds of independent assortments, can also 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 0.05-50wt%;
Described catalyst activity component A, B, C also can be with unsupported form Individual existences;
The mass ratio of reaction raw materials and catalyzer (take active 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, in plant, comprise corn cob, or stalk, and stalk derives from corn, wheat, cotton, Chinese sorghum, soybean, paddy rice, sugarcane, or derive from urban domestic wastewater, timber, forestry waste, recovery paper product.
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:
Method provided by the invention, not only can keep the high yield of Mierocrystalline cellulose catalyzed conversion preparing ethylene glycol, meanwhile, reduces and eliminated the generation of cyclic ethers alcohol byproduct, has reduced the rectifying separation difficulty of ethylene glycol product, has improved the purity of rectifying ethylene glycol product.
Embodiment
Embodiment 1
Get maize straw powder (20-40 order) 10kg, adding water, to make its water content be 30wt%, is placed in 160 ℃ 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, to it, add the NaOH aqueous solution of 50kg concentration 1wt%, at 25 ℃ of room temperatures, soak 12h, after leaching, adding wherein 50kg concentration is the hydrogen peroxide of 1wt%, under room temperature, soak 12h, then clear water rinsing, to neutral, obtains 5kg (dry weight) corn stalk fiber element raw material.
Maize straw powder is replaced with to broomcorn straw, according to the same method above, can obtain corresponding cellulosic material.
Embodiment 2
Get 10.0g corn stalk fiber element (gained in 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 revs/min of stirring velocitys, hydrogen pressure 7MPa in reaction process.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains, gas chromatographic analysis polyvalent alcohol product and cycloalcohol by product yield are opened in pressure release.
Comparative example 1
Get 10.0g corn stalk fiber element (gained in embodiment 1), add 100ml water, 0.1g wolframic acid, 0.1g 5%Ru/AC catalyzer, 0.05g 0.5%Ir/AC in autoclave 250 ℃ react 2h, 500 revs/min of stirring velocitys, hydrogen pressure 7MPa in reaction process.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.
Embodiment 3
Get 10.0g broomcorn straw Mierocrystalline cellulose (gained in embodiment 1) and add 100ml water, 0.1g ammonium metawolframate, 0.1g Raney's nickel catalyst, 0.05g 2%Ru-0.2%Re/SiO
2in autoclave, 240 ℃ are reacted 2h, 500 revs/min of stirring velocitys, hydrogen pressure 7MPa in reaction process.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains, gas chromatographic analysis polyvalent alcohol product and cycloalcohol by product yield are opened in pressure release.
Comparative example 2
Get 10.0g broomcorn straw Mierocrystalline cellulose (gained in embodiment 1) and add 100ml water, 0.1g ammonium metawolframate, 0.1g Raney's nickel catalyst, 0.05g 2%Ru/SiO
2in autoclave, 250 ℃ are reacted 2h, 500 revs/min of stirring velocitys, hydrogen pressure 7MPa in reaction process.After reaction finishes, be down to room temperature, still 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 10.0g Microcrystalline Cellulose and add 100ml water, 0.5g 30%W
2c/AC, 0.1g 1%Rh/AC, 0.05g ReO
2in autoclave, 240 ℃ are reacted 2h, 500 revs/min of stirring velocitys, hydrogen pressure 7MPa in reaction process.After reaction finishes, be down to room temperature, still the centrifugal liquid product that obtains, gas chromatographic analysis polyvalent alcohol product and cycloalcohol by product yield are opened in pressure release.
Comparative example 3
Get 10.0g Microcrystalline Cellulose and add 100ml water, 0.5g 30%W
2c/AC, 0.05g MoO
3in autoclave, 240 ℃ are reacted 2h, 500 revs/min of stirring velocitys, hydrogen pressure 7MPa in reaction process.After reaction finishes, be down to room temperature, still 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 differential responses condition, the product of cellulose conversion preparing ethylene glycol forms and the comparison of yield situation.As shown in Table 1.
The reaction result comparison of cellulose conversion preparing ethylene glycol under table one, different catalysts condition
From the listed result of above form, can see, when the catalyzer reacting for cellulose conversion contains tungsten active ingredient, rhenium active ingredient and hydrogenation activity component simultaneously, the cyclic ethers alcohol by product that reaction process produces contains three kinds of resulting reaction product of active constituent catalyst while being significantly less than difference, embody significant technical progress.
Embodiment 6
The rectifying of ethylene glycol product.The product liquid 1L that extracting cellulose preparing ethylene glycol obtains carries out rectification under vacuum in rectifier unit, and vacuum tightness is 0.1bar, and the theoretical plate number of rectifying column is 10, and reflux ratio is 5.Collect the product of temperature range 120-125C, use gas chromatographic analysis product purity.Products obtained therefrom purity as shown in Table 2.
Cellulose conversion preparing ethylene glycol product rectifying cut purity comparison under table two, different catalysts condition
From table two, can see, the ethylene glycol product obtaining is in the method for the invention after rectifying, and in product, the content of cyclic ethers alcohol, significantly lower than comparative example's result, embodies significant technical progress.In method provided by the invention, adopt ternary component catalyzer, when one-step catalytic transforms preparing ethylene glycol from cellulose, significantly reduce or eliminate cyclic ethers alcohol by product, to reduce the difficulty of ethylene glycol rectification and purification, improve the quality of ethylene glycol product.
Claims (8)
1. one kind is suppressed the method that Mierocrystalline cellulose catalyzed conversion that cyclic ethers alcohol generates is prepared ethylene glycol, it is characterized in that: catalytic hydrogenation reaction process is carried out under agitation condition in closed pressure vessel, temperature of reaction >=150 ℃, 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 and have the active component A of shortening function, the tungstenic active ingredient B with catalyse cellulose degradation function and rhenium-containing catalytic active component C, 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; The metal active composition of catalyst A and the activeconstituents of catalyzer C, the activeconstituents of C is with rhenium metal weighing scale, and weight ratio is between 0.02-3000 times of scope.
2. it is characterized in that in accordance with the method for claim 1: in catalyzer used, contain and there is the active component A of shortening function, the tungstenic active ingredient B with catalyse cellulose degradation function and rhenium-containing catalytic active component C; 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, the oxide compound of tungsten, wolfram varbide, tungsten nitride, tungsten phosphide, tungsten, the muriate of the sulfide of tungsten, tungsten, one or more in the oxyhydroxide of tungsten, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxotungstate, heteropoly tungstic acid; Rhenium-containing catalytic active component C comprise rhenium metal, rhenium+1 ,+2 ,+3 ,+4 ,+5 ,+6, one or both in+7 valence state oxide compounds;
Described catalyst activity component A and active ingredient B, active ingredient C can three kinds be supported on porous support jointly, also can jointly be supported on porous support by any two kinds of independent assortments, can also 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%;
Described catalyst activity component A, B, C also can be with unsupported form Individual existences.
3. in accordance with the method for claim 1, it is characterized in that: the activeconstituents weight ratio preferable range of the metal active composition of catalyst A and catalyst B is between 0.05-100 times, and wherein the weight of B activeconstituents is with tungsten weighing scale.
4. in accordance with the method for claim 1, it is characterized in that: the activeconstituents weight ratio preferable range of the metal active composition of catalyst A and catalyzer C is between 0.1-100 times of scope, and wherein the activeconstituents of catalyzer C is with rhenium metal weighing scale.
5. in accordance with the method for claim 1, it is characterized in that: range of reaction temperature is at 150-350 ℃, the pressure 3-10 MPa of preferred hydrogen in reaction process, the preferred reaction time is 30 min – 3 h, the mass ratio of reaction raw materials and catalyzer is 1:1-30000:1, wherein, the quality of catalyzer is in active metal quality.
6. in accordance with the method for claim 5, it is characterized in that: reaction raw materials is 3:1-3000:1 with the quality of catalyzer than preferable range, and wherein, the quality of catalyzer is in active metal quality.
7. in accordance with the method for claim 5, it is characterized in that preferred temperature of reaction is 220-280 ℃, the preferred scope of mass ratio of reaction raw materials and catalyzer is 4:1-1000:1, and wherein, the quality of catalyzer is in active metal quality.
8. in accordance with the method for claim 1, it is characterized in that: described fibrin reaction raw material sources are in corn cob, or stalk, stalk derives from corn, wheat, cotton, Chinese sorghum, soybean, paddy rice, sugarcane, or derives from urban domestic wastewater, timber, forestry waste, recovery paper product.
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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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Non-Patent Citations (4)
| Title |
|---|
| Ming-Yuan Zheng et al..Transition Metal-Tungsten Bimetallic Catalysts for the Conversion of Cellulose into Ethylene Glycol.《ChemSusChem》.2010,第3卷(第1期),63-66. |
| Transition Metal-Tungsten Bimetallic Catalysts for the Conversion of Cellulose into Ethylene Glycol;Ming-Yuan Zheng et al.;《ChemSusChem》;20100125;第3卷(第1期);63-66 * |
| 乙二醇制备方法的专利技术进展及评述;赵凤阁;《精细与专用化学品》;201107;第19卷(第7期);38-41 * |
| 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》.2011,第19卷(第7期),38-41. |
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