CN102731255B - Method for preparing glycol by using corncobs as raw materials - Google Patents
Method for preparing glycol by using corncobs as raw materials Download PDFInfo
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002994 raw material Substances 0.000 title claims abstract description 26
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010937 tungsten Substances 0.000 claims abstract description 27
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 239000010948 rhodium Substances 0.000 claims abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 240000008042 Zea mays Species 0.000 claims description 41
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 41
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 37
- 235000005822 corn Nutrition 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000001913 cellulose Substances 0.000 claims description 21
- 229920002678 cellulose Polymers 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004904 shortening Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000010974 bronze Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- -1 tungsten nitride Chemical class 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 238000004880 explosion Methods 0.000 abstract description 15
- 239000002028 Biomass Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000002203 pretreatment Methods 0.000 abstract description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract 1
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 19
- 239000000047 product Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000012263 liquid product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010902 straw Substances 0.000 description 5
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 235000009973 maize Nutrition 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 240000006394 Sorghum bicolor Species 0.000 description 3
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 235000015505 Sorghum bicolor subsp. bicolor Nutrition 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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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| 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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