CN102464637B - Method and device for preparing 5-hydroxymethyl furaldehyde - Google Patents
Method and device for preparing 5-hydroxymethyl furaldehyde Download PDFInfo
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Abstract
The invention relates to a method and a device for preparing 5-hydroxymethyl furaldehyde. The device comprises a reaction area, a boiling area and a distilling area, wherein the reaction area comprises a first organic layer and a second organic layer; the first organic layer comprises saccharides and a solvent; the second organic layer comprises a solvent composition with azeotrope and extraction functions; the boiling area is connected with the reaction area and comprises mixed solution consisting of the 5-hydroxymethyl furaldehyde and the solvent composition; the distilling area is connected with the reaction area and comprises a water layer and a liquid layer; and the liquid layer comprises the solvent composition. The invention also provides the method for preparing the 5-hydroxymethyl furaldehyde.
Description
Technical field
The present invention relates to prepare the device and method of 5 hydroxymethyl furfural.
Background technology
At present, the whole world is faced with gradually and the earth atmosphere Greenhouse effect lasting problem that expand exhausted by exploitation of reserves of oil amount.Europe, the United States, day etc. country formulated the year two thousand twenty plastic cement consumption market product section ratio must be from the policy of renewable resources, the research that extracts industrial chemicals from raw raw material is come into one's own.American-European countries is in the exploitation of BREW and BIOMASS biomass energy is planned, by 5 hydroxymethyl furfural (5-hydroxymethylfurfural, HMF) with its derivative 2,5-furandicarboxylic acid (2,5-Furandicarboxylic acid, FDCA) classify the initial chemical of important ring-type (building block) of the raw matter plastic cement products application of furans polyester (Furanic Polyesters) and furans polymeric amide (Furanic Polyamides) as.The downstream derivatives intermediates product of 5 hydroxymethyl furfural (HMF) comprising: the chemical intermediates of (1) tetrahydrofuran (THF) (Tetrahydrofuran); (2) the synthetic raw material of enamel paint or the solvent of resin; And the synthesis material of (3) organic synthesis raw material, especially pyrroles (Pyrrole) and thiophene (Thiophene).The following raw material of manufacturing 5 hydroxymethyl furfural (HMF) is to estimate that the carbohydrate of producing take the biological hydrolysis of Mierocrystalline cellulose commercial technology in 2015 is as source.
5 hydroxymethyl furfural belongs to furfural class, and it can suppress microbial growth in solution, therefore, cannot be synthetic with biological fermentation process, only can be transformed by hexose with chemical method.But because its side reaction is wayward and 5 hydroxymethyl furfural is difficult for separation and purification, cause that reaction efficiency is low and production cost is too high, so that its downstream application product loses the chance of marketing.The reason that 5 hydroxymethyl furfural production efficiency is low comprises: (1) 5 hydroxymethyl furfural can aggregate into humin substances under high temperature and sour environment; (2) 5 hydroxymethyl furfural can hydrolysis generate levulinic acid under acidic aqueous solution and hot environment; And (3) 5 hydroxymethyl furfural under hot environment can with carbohydrate intersect aldol condensation (crossed aldol) react generation humin substances.
The method of the synthetic 5 hydroxymethyl furfural of Lewkowski (ARKIVOC 2001) summary four classes comprises: (1) reacts manufacture method lower than the homogeneous phase aqueous solution of 200 ℃; (2) react manufacture method higher than the homogeneous phase aqueous solution of 200 ℃; (3) organic solution reaction manufacture method; And (4) two phase reaction manufacture method.Lower than the homogeneous phase aqueous solution reaction method of 200 ℃, the productive rate of its 5 hydroxymethyl furfural is only 30%, and higher than the homogeneous phase aqueous solution reaction method of 200 ℃, the maximum output of its 5 hydroxymethyl furfural also only reaches 58%.In above cubic method, organic solution reaction manufacture method is for avoiding 5 hydroxymethyl furfural hydrolysis to generate levulinic acid.Szmant delivered with boron trifluoride diethyl etherate title complex (BF in 1981
3et
2o) for catalyzer, carbohydrate is placed in to dimethyl sulfoxide (DMSO) (Dimethyl Sulfoxide, DMSO) in, the method (J.Chem.Tech.Biotechnol.) of synthetic 5 hydroxymethyl furfural, wherein only has fructose can obtain the productive rate that is greater than 90%.But boron trifluoride diethyl etherate title complex is corrosive, high unit price, can not reuse and the problem that produces waste water, and 5 hydroxymethyl furfural is difficult to separate from dimethyl sulfoxide (DMSO) (DMSO), thereby cannot commercialization.Archer-Daniels-Midland Co. (US 7,317,116B2,2008) with high fructose syrups at METHYLPYRROLIDONE (N-Methyl-2-Pyrrolidone, or N,N-DIMETHYLACETAMIDE (Dimethylacetamide NMP), DMAc) in solid acid catalysis under synthetic 5 hydroxymethyl furfural, but also exist 5 hydroxymethyl furfural from METHYLPYRROLIDONE (NMP) separate complex and difficult problem.In above four kinds of methods, two phase reaction method is to go out 5 hydroxymethyl furfural from 177 ℃ containing continuous extraction the water of mineral acid with water-fast organic solvent, to promote principal product productive rate.But the method must be used a large amount of organic solvents to extract and must drop into the considerable energy and isolate 5 hydroxymethyl furfural from thin 5 hydroxymethyl furfural mixed solution, and still has the problem of corrosion.
Reduce side reaction and set up can business-like technology for reaching, the research institutions such as well-known chemical company and Battelle, Wisconsin such as external existing such as Dupont, Merk & Co, Canon KK, FURCHIM, Roquette attempt respectively how breaking through 5 hydroxymethyl furfural productive rate technology barrier on the low side.Wherein (the US 4 of Roquette company, 590, 283, 1986) 20% fructose is placed in to dimethyl sulfoxide (DMSO) (DMSO) using the acid of AMBERLIT C200 resin cation (R.C.) as catalyzer, react simultaneously with methyl iso-butyl ketone (MIBK) (Methyl Isobutyl ketone at 80 ℃, MIBK) extraction 5 hydroxymethyl furfural, the 5 hydroxymethyl furfural obtaining, its productive rate is up to 97%, but, reaction must expend 8 hours, especially the 5 hydroxymethyl furfural content of methyl iso-butyl ketone (MIBK) (MIBK) is too rare, only there are 2 % by weight, and must reclaim a large amount of solvents, increase considerable production cost.And Wisconsin university adds solubilized 5 hydroxymethyl furfural in water react and form two phase reaction with the immiscible organic solvent of water simultaneously, contact the probability of hydrolysis generation levulinic acid (Levulinic acid) with water to reduce 5 hydroxymethyl furfural.But, although its reaction of the method only must 3 minutes, the productive rate of 5 hydroxymethyl furfural only approximately 75%.
Summary of the invention
One embodiment of the present of invention provide a kind of device of preparing 5 hydroxymethyl furfural, this device comprises: reaction zone, comprising the first organic layer and the second organic layer, wherein this first organic layer comprises carbohydrate and solvent, this second organic layer comprises the solvent compositions that has azeotropic, extracts and suppress side reaction function, in this first organic layer, this carbohydrate generates 5 hydroxymethyl furfural and water through dehydration reaction, and this solvent compositions is extracted to this 5 hydroxymethyl furfural in this second organic layer; What be connected with this reaction zone boils district, comprising the mixing solutions being formed by this 5 hydroxymethyl furfural, by product and this solvent compositions, forms the first steam and enter this reaction zone after boiling, and this of this reaction zone the second organic layer is back to this and boils district; And the rectification zone being connected with this reaction zone, comprising water and liquid level, wherein this liquid level comprises this solvent compositions, and the water in this reaction zone and this first steam are mixed to form the second steam and enter this rectification zone, and this liquid level is back to this second organic layer of this reaction zone.
One embodiment of the present of invention provide a kind of preparation method of 5 hydroxymethyl furfural, and the method comprises: prepare saccharide solution, this saccharide solution comprises carbohydrate and solvent; This saccharide solution is flowed into reaction zone, to form the first organic layer; Solvent compositions is poured into and boiled district and boil, enter this reaction zone to form the first steam, form the second organic layer; In this first organic layer, this carbohydrate generates 5 hydroxymethyl furfural and water through dehydration reaction, and this solvent compositions is extracted to this 5 hydroxymethyl furfural in this second organic layer; Mix water and this first steam in this reaction zone, enter rectification zone to form the second steam, to form water and liquid level in this rectification zone, wherein this liquid level comprises this solvent compositions; This liquid level is back to this second organic layer of this reaction zone; This second organic layer of this reaction zone is back to this and boils district, to boil at this mixing solutions that in district, formation is formed by this 5 hydroxymethyl furfural and this solvent compositions; Boil in district at this, this mixing solutions is boiled, enter this reaction zone to form this first steam; And cooling this boil unevaporated this mixing solutions in district, to be divided into the 3rd organic layer that is rich in this solvent compositions and the 4th organic layer that is rich in this 5 hydroxymethyl furfural.
Change into the productive rate of 5 hydroxymethyl furfural through dehydration reaction for improving hexose, the solution of the present invention after with organic solvent dissolution carbohydrate continuously flows into the chemical reaction equipment that contains catalyzer.This device can extract 5 hydroxymethyl furfural principal product and remove the water of generation with azeotropic principles when reaction generates 5 hydroxymethyl furfural, so, can obtain the 5 hydroxymethyl furfural of high yield.
Accompanying drawing explanation
Fig. 1 according to one embodiment of present invention, discloses a kind of device and method of preparing 5 hydroxymethyl furfural.Wherein main element nomenclature is as follows:
100～device;
102～reaction zone;
104～boil district;
106～rectification zone;
108～the first organic layers;
110～the second organic layers;
112～mixing solutions;
The 113～three organic layer;
The 114～four organic layer;
116～the first steams;
118～the second steams;
120～water;
122～liquid level;
124～condenser;
126～saccharide solution.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, below specially enumerate preferred embodiment, be described in detail below:
Refer to Fig. 1, according to one embodiment of present invention, disclose a kind of device of preparing 5 hydroxymethyl furfural.Device 100 comprises reaction zone 102, boils district 104 and rectification zone 106.Reaction zone 102 comprises the first organic layer 108 and the second organic layer 110.The first organic layer 108 comprises carbohydrate, solvent and catalyzer.The second organic layer 110 comprises solvent compositions.In the first organic layer 108, carbohydrate generates 5 hydroxymethyl furfural and water through dehydration reaction, and solvent compositions is extracted to 5 hydroxymethyl furfural in the second organic layer 110.But along with the difference that solvent is selected, above-mentioned each organic layer density can change, and allows HMF have an opportunity at the first organic layer or the second organic layer.
Boiling district 104 is connected with reaction zone 102.Boil district 104 and comprise the mixing solutions 112 being formed by 5 hydroxymethyl furfural and solvent compositions.Mixing solutions 112 forms the first steam 116 and enters reaction zone 102 after boiling.Can be used as reaction zone 102 carrying out carbohydrate required thermal source while generating the dehydration reaction of 5 hydroxymethyl furfural from boiling the first steam 116 that district 104 imports.The second organic layer 110 of reaction zone 102 is back to and boils district 104.Unevaporated mixing solutions 112 is divided into the 3rd organic layer 113 and the 4th organic layer 114 that is rich in 5 hydroxymethyl furfural that are rich in solvent compositions after cooling.But, the difference of selecting with solvent, above-mentioned each organic layer density can change, and allows HMF have an opportunity at the 3rd organic layer or the 4th organic layer.
Rectification zone 106 is connected with reaction zone 102.Rectification zone 106 comprises water and liquid level.Liquid level comprises solvent compositions.The water generating through dehydration reaction in reaction zone 102 and the first steam 116 are mixed to form the second steam 118 and enter rectification zone 106.Water 120 flows out from rectification zone 106.Liquid level 122 is back to the second organic layer 110 of reaction zone 102.Rectification zone 106 more comprises condenser 124, with condensation the second steam 118, forms water 120 and liquid level 122.
In the first organic layer 108, carbohydrate can comprise glucose, sucrose, fructose or high fructose syrups, solvent can be aprotic polar solvent, for example dimethyl sulfoxide (DMSO) (Dimethyl Sulfoxide, DMSO), N,N-DIMETHYLACETAMIDE (Dimethylacetamide, DMAc), dimethyl formamide (Dimethylformamide, or METHYLPYRROLIDONE (N-Methyl-2-Pyrrolidone DMF), NMP), catalyzer can comprise for example acidic ion exchange resin, zeolite (zeolite) or heteropolyacid (heteropolyacids, HPA) solid-phase catalyst or for example Lewis acid (Lewis acids), ammonium chloride (NH
4cl), the homogeneous catalyst of chlorination organic ammonium salt, salt acid metal salt, nitric acid metal-salt, phosphate metal salt or sulfuric acid metal-salt.If the catalyzer of above-mentioned use is homogeneous catalyst, first in charging, prepare, if solid-phase catalyst is first seated in reaction zone.
The above-mentioned solvent compositions with azeotropic and extraction function is by having and the dimethyl sulfoxide (DMSO) (DMSO) of the first organic layer 108, N,N-DIMETHYLACETAMIDE (DMAc), dimethyl formamide (DMF) or METHYLPYRROLIDONE (NMP) difficulty mix, but can (can comprise alkanes or chlorination alkanes with the solvent of water generates minimum azeotrope dot characteristics, be preferably the alkanes of carbon number 7～8), have and can not (can comprise ester class with the dissolve each other solvent of characteristic of water, ketone, ethers or Benzene Chloride class, be preferably ester class or ketone, the ketone of for example acetic acid alkyl (carbon number 2～4) ester class or carbon number 4～6) or its combination, form according to azeotropic and the performance proportioning that needs of extraction function.
Reaction zone 102 can be the liquid accumulation area being made up of multiple distillation plates and plate spacing thereof, or is made up of the flash tank of one or more tandem gas-to-liquid contact.Rectification zone 106 can be made up of multiple distillation plates or packing layer.
The device that the present invention prepares 5 hydroxymethyl furfural be divided into boil, the boiling district, carry out dehydration reaction hold concurrently reaction zone and dehydration rectification zone three parts of 5 hydroxymethyl furfural extraction of evaporating solvent composition, with three kinds of functions such as reach carbohydrate dehydration, 5 hydroxymethyl furfural extraction and dewater simultaneously.Carry out hold concurrently reaction zone and the rectification zone of 5 hydroxymethyl furfural extraction of dehydration reaction and be positioned at tower device.Carbohydrate/solvent is from the Lower Half charging of tower device, in Lower Half (carry out dehydration reaction hold concurrently 5 hydroxymethyl furfural extraction), contacts and be heated and carry out dehydration reaction with the first steam, and it has equilibrium temperature (80～130 ℃).Carbohydrate/solvent is insoluble to the second organic layer (solvent compositions) and forms two liquid layers.Carbohydrate generates 5 hydroxymethyl furfural through dehydration reaction, and 5 hydroxymethyl furfural is dissolved into the second organic layer.Catalyzer exists only in the first organic layer, is not dissolved into the second organic layer to avoid 5 hydroxymethyl furfural to produce self condensation reaction and hydrolysis reaction.The solvent compositions of the water generating after dehydration reaction and the first steam produces azeotropic steam (the second steam) and flies to alter toward the first half of tower device, through the tower top (104～115 ℃) of rectification zone again to condenser condenses, be divided into two liquid phases, upper liquid layer (liquid level) is solvent compositions, carry out total reflux, lower liquid layer is water-enriched layer, flow to receiving flask.In the Lower Half of tower device, flow into and boil district containing the second organic layer of solvent compositions and 5 hydroxymethyl furfural.Solvent compositions flashes to the first steam again gets back to the bottom of tower device.The 5 hydroxymethyl furfural product solution of high density is boiling district's generation (be divided into the liquid layer that is rich in solvent compositions and the liquid layer that is rich in 5 hydroxymethyl furfural after cooling, the liquid layer that is rich in 5 hydroxymethyl furfural is approximately 90～130 mg/ml containing the concentration of 5 hydroxymethyl furfural).
Still refer to Fig. 1, disclose according to one embodiment of present invention a kind of preparation method of 5 hydroxymethyl furfural, comprise the following steps.First, prepare saccharide solution 126.Saccharide solution 126 comprises carbohydrate, solvent and catalyzer.In one embodiment, the present invention utilizes the aprotic polar solvent of the meeting dissolving hexoses such as such as dimethyl sulfoxide (DMSO) (DMSO), N,N-DIMETHYLACETAMIDE (DMAc), dimethyl formamide (DMF) or METHYLPYRROLIDONE (NMP) or sucrose to be mixed with the saccharide solution of 1～30 % by weight.Saccharide solution 126 is flowed into reaction zone 102, to form the first organic layer 108.Solvent compositions is poured into and boiled district 104 and boil, enter reaction zone 102 to form the first steam 116, form the second organic layer 110.In the first organic layer 108, under catalyzer exists, carbohydrate generates 5 hydroxymethyl furfural and water through dehydration reaction, and solvent compositions is extracted to 5 hydroxymethyl furfural in the second organic layer 110.The water and the first steam 116 that in hybrid reaction district 102, generate through dehydration reaction, enter rectification zone 106 to form the second steam 118, to form water and liquid level in rectification zone 106.Liquid level comprises solvent compositions.Collect the water 120 flowing out from rectification zone 106.Liquid level 122 is back to the second organic layer 110 of reaction zone 102.The second organic layer 110 of reaction zone 102 is back to and boils district 104, with boiling the mixing solutions 112 that in district 104, formation is formed by 5 hydroxymethyl furfural and solvent compositions.Mixing solutions 112 enters reaction zone 102 to form the first steam 116 after boiling.Collect unevaporated mixing solutions 112, after cooling, be divided into the 3rd organic layer 113 that is rich in solvent compositions, with the 4th organic layer 114 that is rich in 5 hydroxymethyl furfural.
In saccharide solution 126, carbohydrate can comprise glucose, sucrose, fructose or high fructose syrups, solvent can be aprotic polar solvent, for example dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, dimethyl formamide or METHYLPYRROLIDONE, catalyzer can comprise the solid-phase catalyst of for example acidic ion exchange resin, zeolite or heteropolyacid or for example Lewis acid, ammonium chloride (NH
4cl), the homogeneous catalyst of chlorination organic ammonium salt, salt acid metal salt, nitric acid metal-salt, phosphate metal salt or sulfuric acid metal-salt.If the catalyzer of above-mentioned use is homogeneous catalyst, first in charging, prepare, if solid-phase catalyst is first seated in reaction zone.
The above-mentioned solvent compositions with azeotropic and extraction function is by having and the dimethyl sulfoxide (DMSO) (DMSO) of the first organic layer 108, N,N-DIMETHYLACETAMIDE (DMAc), dimethyl formamide (DMF) or METHYLPYRROLIDONE (NMP) difficulty mix, but can with the solvent of water generates minimum azeotrope dot characteristics, can comprise alkanes or chlorination alkanes, be preferably the alkanes of carbon number 7～8, with have can not with the dissolve each other solvent of characteristic of water, can comprise ester class, ketone, ethers or Benzene Chloride class, be preferably ester class or ketone, the ketone of for example acetic acid alkyl (carbon number 2～4) ester class or carbon number 4～6, form according to azeotropic and the performance proportioning that needs of extraction function.
Reaction zone 102 can be the liquid accumulation area being made up of multiple distillation plates and plate spacing thereof, or is made up of the flash tank of one or more tandem gas-to-liquid contact.Rectification zone 106 can be made up of multiple distillation plates or packing layer.
In above-mentioned saccharide solution 126, the shared weight percent of carbohydrate is substantially between 1～30 % by weight.In the second organic layer 110, when solvent compositions is containing alkanes, while containing chlorination alkanes, the ratio of one or more in chlorination alkanes and ester class, ketone, ethers, Benzene Chloride class is between (, (chlorination alkanes)/(one or more in ester class, ketone, ethers, Benzene Chloride class)=1: 1～1: 0) between 1: 1～1: 0; In the time that solvent compositions contains alkanes, the ratio of one or more in alkanes and ester class, ketone, ethers, Benzene Chloride class, chlorination alkanes is between (, (alkanes)/(one or more in ester class, ketone, ethers, Benzene Chloride class, chlorination alkanes)=1: 1～1: 0) between 1: 1～1: 0.Described ratio is preferably between 1: 1～3: 1.The temperature of above-mentioned dehydration reaction is substantially between 80～150 ℃, and the time of dehydration reaction is substantially between 10 minutes to 3 hours, preferably between 20 minutes to 2 hours.The temperature at 106 tops, rectification zone is substantially between 104～115 ℃.The part by weight of ester class, ketone, ethers or Benzene Chloride class and the aprotic polar solvent of solvent compositions is approximately 1: 2.There is azeotropic and can form minimum boiling point with solvent compositions and the aprotic polar solvent of extraction function, easily separate with 5 hydroxymethyl furfural.
Change into the productive rate of 5 hydroxymethyl furfural through dehydration reaction for improving hexose, the solution of the present invention after with organic solvent dissolution carbohydrate continuously flows into the chemical reaction equipment that contains catalyzer.This device can extract 5 hydroxymethyl furfural principal product and remove the water of generation with azeotropic principles when reaction generates 5 hydroxymethyl furfural, so, can obtain the 5 hydroxymethyl furfural of high yield.
[embodiment 1]
The preparation (1) of 5 hydroxymethyl furfural
The isobutyl acetate of the octane of 256 grams and 125 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, will contain 20.0 grams of fructose, 1.56 grams of ammonium chloride (NH
4cl) (catalyzer) reacts with the flow inflow reaction zone of 8.1 ml/min with the saccharide solution of 80.12 grams of dimethyl sulfoxide (DMSO) (DMSO).Complete charging in 50 seconds in the 10th minute.Now, the temperature of boiling district is 122 ℃, and the temperature of reaction zone is 116 ℃, and the tower top temperature of dehydration rectification zone is 109 ℃.At the 31st minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 95 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 101 mg/ml.Calculating transformation efficiency by fructose residual volume is 99.4%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 34.5 grams, and the first organic layer is 71.2 grams, and calculating the 5 hydroxymethyl furfural generating is 10.399 grams, and the productive rate of 5 hydroxymethyl furfural is 74.6 % by mole.
[embodiment 2]
The preparation (2) of 5 hydroxymethyl furfural
The isobutyl acetate of the normal heptane of 223 grams and 106 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, will contain 20.2 grams of fructose, 1.554 grams of ammonium chloride (NH
4cl) (catalyzer) reacts with the flow inflow reaction zone of 8.1 ml/min with the saccharide solution of 83.69 grams of dimethyl sulfoxide (DMSO) (DMSO).Complete charging in the 12nd minute.Now, the temperature of boiling district is 103 ℃, and the temperature of reaction zone is 99 ℃, and the tower top temperature of dehydration rectification zone is 96 ℃.At the 60th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 55 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 129 mg/ml.Calculating transformation efficiency by fructose residual volume is 99.9%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 41.8 grams, and the first organic layer is 64.5 grams, and calculating the 5 hydroxymethyl furfural generating is 10.323 grams, and the productive rate of 5 hydroxymethyl furfural is 73.4 % by mole.
[embodiment 3]
The preparation (3) of 5 hydroxymethyl furfural
The isobutyl acetate of the octane of 200 grams and 154 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, will contain 20.5 grams of fructose, 1.10 grams of iron(ic) chloride (FeCl
3) saccharide solution of (catalyzer) and 80.11 grams of dimethyl sulfoxide (DMSO) (DMSO) flows into reaction zone with the flow of 4.1 ml/min and react.Complete charging in 30 seconds in the 20th minute.Now, the temperature of boiling district is 121 ℃, and the temperature of reaction zone is 119 ℃, and the tower top temperature of dehydration rectification zone is 115 ℃.At the 45th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 94 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 69 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 77.0 grams, and the first organic layer is 56.1 grams, and calculating the 5 hydroxymethyl furfural generating is 10.541 grams, and the productive rate of 5 hydroxymethyl furfural is 73.8 % by mole.
[embodiment 4]
The preparation (4) of 5 hydroxymethyl furfural
The methyl iso-butyl ketone (MIBK) (MIBK) of the octane of 228 grams and 153 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 8.88 grams of Amberlyt-35 (catalyzer) and react with the flow of 4.1 ml/min with the saccharide solution of 80.53 grams of dimethyl sulfoxide (DMSO) (DMSO) containing 20.0 grams of fructose.Complete charging in 25 seconds in the 19th minute.Now, the temperature of boiling district is 120 ℃, and the temperature of reaction zone is 115 ℃, and the tower top temperature of dehydration rectification zone is 108 ℃.At the 42nd minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 85 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 39 mg/ml.Calculating transformation efficiency by fructose residual volume is 99.4%.The content of separately analyzing 5 hydroxymethyl furfural in the 3rd organic layer take GC is as 2.5 mg/ml, and in the second organic layer, the content of 5 hydroxymethyl furfural is 0.1 mg/ml.The 4th organic layer is through being weighed as 80.28 grams, and the first organic layer is 81.3 grams, and calculating the 5 hydroxymethyl furfural generating is 10.564 grams, and the productive rate of 5 hydroxymethyl furfural is 75.6 % by mole.
[embodiment 5]
The preparation (5) of 5 hydroxymethyl furfural
The octane of 294 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 8.9 grams of Amberlyt-35 (catalyzer) and react with the flow of 5.1 ml/min with the saccharide solution of 80.31 grams of dimethyl sulfoxide (DMSO) (DMSO) containing 20.1 grams of fructose.Complete charging in 10 seconds in the 16th minute.Now, the temperature of boiling district is 129 ℃, and the temperature of reaction zone is 123 ℃, and the tower top temperature of dehydration rectification zone is 117 ℃.At the 165th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 326 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 120 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 80.29 grams, and the first organic layer is 77.31 grams, and calculating the 5 hydroxymethyl furfural generating is 11.493 grams, and the productive rate of 5 hydroxymethyl furfural is 82.3 % by mole.
[embodiment 6]
The preparation (6) of 5 hydroxymethyl furfural
The isobutyl acetate of the octane of 225 grams and 154 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 8.84 grams of Amberlyt-35 (catalyzer) and react with the flow of 5.1 ml/min with the saccharide solution of 79.96 grams of dimethyl sulfoxide (DMSO) (DMSO) containing 20.0 grams of fructose.Complete charging in 15 seconds in the 20th minute.Now, the temperature of boiling district is 122 ℃, and the temperature of reaction zone is 118 ℃, and the tower top temperature of dehydration rectification zone is 108 ℃.At the 60th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 81 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 52 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 92.7 grams, and the first organic layer is 56.7 grams, and calculating the 5 hydroxymethyl furfural generating is 9.856 grams, and the productive rate of 5 hydroxymethyl furfural is 70.7 % by mole.
[embodiment 7]
The preparation (7) of 5 hydroxymethyl furfural
The octane of 365 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 8.95 grams of Amberlyt-35 (catalyzer) and react with the flow of 8.1 ml/min with the saccharide solution of 76.98 grams of N,N-DIMETHYLACETAMIDEs (DMAc) containing 20.1 grams of fructose.Complete charging in 40 seconds in the 11st minute.Now, the temperature of boiling district is 127 ℃, and the temperature of reaction zone is 122 ℃, and the tower top temperature of dehydration rectification zone is 119 ℃.At the 51st minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 118 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 58 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 49.8 grams, and the first organic layer is 46.2 grams, and calculating the 5 hydroxymethyl furfural generating is 8.628 grams, and the productive rate of 5 hydroxymethyl furfural is 61.7 % by mole.
[embodiment 8]
The preparation (8) of 5 hydroxymethyl furfural
The isobutyl acetate of the octane of 235.07 grams and 115.9 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 8.88 grams of DOWEX 50WX8-100 (catalyzer) and react with the flow of 4.1 ml/min with the saccharide solution of 80.88 grams of dimethyl sulfoxide (DMSO) (DMSO) containing 20.08 grams of fructose.Complete charging in the 20th minute.Now, the temperature of boiling district is 122 ℃, and the temperature of reaction zone is 119 ℃, and the tower top temperature of dehydration rectification zone is 111 ℃.At the 60th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 102.6 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 57.5 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 74.2 grams, and the first organic layer is 74.9 grams, and calculating the 5 hydroxymethyl furfural generating is 11.0 grams, and the productive rate of 5 hydroxymethyl furfural is 78.7 % by mole.
[embodiment 9]
The preparation (9) of 5 hydroxymethyl furfural
The isobutyl acetate of the octane of 235.06 grams and 116.67 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, the saccharide solution that will contain 19.97 grams of fructose and 80.21 grams of dimethyl sulfoxide (DMSO) (DMSO) flows into containing 8.92 grams of HPA-DW (H with the flow of 4.1 ml/min
3w
12o
40) reaction zone of (catalyzer) reacts.Complete charging in the 20th minute.Now, the temperature of boiling district is 120 ℃, and the temperature of reaction zone is 115 ℃, and the tower top temperature of dehydration rectification zone is 105 ℃.At the 50th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 94.6 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 52.6 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 75.8 grams, and the first organic layer is 77 grams, and calculating the 5 hydroxymethyl furfural generating is 10.23 grams, and the productive rate of 5 hydroxymethyl furfural is 73.6 % by mole.
[embodiment 10]
The preparation (10) of 5 hydroxymethyl furfural
By 100 grams of tungstophosphoric acids (12-Tungstophosphoric acid, H
3pO
4-12WO
3, purchased from Showa) hold in the palm in vacuum 1,100 ℃ are heated 8 hours, form anhydrous tungstophosphoric acid; Then 50 grams of anhydrous tungstophosphoric acids are dissolved in 250 ml deionized water, form the tungstophosphoric acid aqueous solution.7.07 grams of cesium carbonates are dissolved in 50 grams of deionized waters, form cesium carbonate aqueous solution.Cesium carbonate aqueous solution is slowly splashed in the tungstophosphoric acid aqueous solution, form white casse precipitation, leave standstill after 16 hours, filter and obtain white solid.Within 16 hours, obtain heteropolyacid catalyst CS-HPA-PW (molecular formula is Cs dry in 110 ℃ of baking ovens this white solid
3pW
12o
40).
The isobutyl acetate of the octane of 237.63 grams and 115.6 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 8.93 grams of CS-HPA-PW and react with the flow of 4.1 ml/min with the saccharide solution of 80.57 grams of dimethyl sulfoxide (DMSO) (DMSO) containing 20.06 grams of fructose.Complete charging in the 20th minute.Now, the temperature of boiling district is 121 ℃, and the temperature of reaction zone is 116 ℃, and the tower top temperature of dehydration rectification zone is 107 ℃.At the 70th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 80.4 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 50.4 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 83.57 grams, and the first organic layer is 74.3 grams, and calculating the 5 hydroxymethyl furfural generating is 9.676 grams, and the productive rate of 5 hydroxymethyl furfural is 69.3 % by mole.
[embodiment 11]
The preparation (11) of 5 hydroxymethyl furfural
2.3 liters of Amberlyst 131 resins are put in jacketed glass groove reactor.Take 5.756
Gram Mercaptamine (Cysteamine Hydrochloride), is dissolved in 1200 grams of deionized waters, adds in above-mentioned jacketed glass groove after to be dissolved, stirs 4 hours at 80 ℃, then filters.After filtration, add 7.5 liters of deionized waters to filter cake resin, stirring at normal temperature clean, repeats to add for 3 times at every turn 7.5 liters of washed with de-ionized water and filtration after obtain azochlorosulfonate acid resin catalyst.
The isobutyl acetate of the octane of 236.4 grams and 115.9 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 9.55 grams of azochlorosulfonate acid resin catalysts and react with the flow of 4.1 ml/min with the saccharide solution of 80.23 grams of dimethyl sulfoxide (DMSO) (DMSO) containing 20.00 grams of fructose.Complete charging in the 20th minute.Now, the temperature of boiling district is 122 ℃, and the temperature of reaction zone is 116 ℃, and the tower top temperature of dehydration rectification zone is 111 ℃.At the 70th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 80.4 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 50.4 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 86.55 grams, and the first organic layer is 89.49 grams, and calculating the 5 hydroxymethyl furfural generating is 10.03 grams, and the productive rate of 5 hydroxymethyl furfural is 72.1 % by mole.
[embodiment 12]
The preparation (12) of 5 hydroxymethyl furfural
The Di Iso Propyl Ether (Diisopropylether) of the octane of 235.95 grams and 115.66 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 8.84 grams of Amberlyt-35 (catalyzer) and react with the flow of 5.1 ml/min with the saccharide solution of 82.2 grams of dimethyl sulfoxide (DMSO) (DMSO) containing 20.11 grams of fructose.Complete charging in 15 seconds in the 20th minute.Now, the temperature of boiling district is 116 ℃, and the temperature of reaction zone is 93 ℃, and the tower top temperature of dehydration rectification zone is 67 ℃.At the 70th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 162 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 64 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 13.8 grams, and the first organic layer is 121 grams, and calculating the 5 hydroxymethyl furfural generating is 8.967 grams, and the productive rate of 5 hydroxymethyl furfural is 64.1 % by mole.
[embodiment 13]
The preparation (13) of 5 hydroxymethyl furfural
The octane of 237 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, by containing 20.15 grams of sucrose, 5 grams of water flow into containing the reaction zone of 8.84 grams of Amberlyt-35 (catalyzer) and react with the flow of 5.1 ml/min with the saccharide solution of 75.05 grams of dimethyl sulfoxide (DMSO) (DMSO).Complete charging in the 23rd minute.Now, the temperature of boiling district is 129 ℃, and the temperature of reaction zone is 122 ℃, and the tower top temperature of dehydration rectification zone is 117 ℃.Reaction overhead water total reflux before the 40th minute, to provide water to make sucrose hydrolysis, afterwards, then is discharged the water layer of tower top phase splitter.At the 100th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 139 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 35 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 2.4 grams, and the first organic layer is 147.78 grams, and calculating the 5 hydroxymethyl furfural generating is 4.977 grams, and the productive rate of 5 hydroxymethyl furfural is 35.3 % by mole.
[embodiment 14]
The preparation (14) of 5 hydroxymethyl furfural
The octane of 239.9 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, to contain 30.85 grams of high fructose syrupss (good year fructose: 75% sugar, sugared content is respectively 90% fructose, 5% glucose, 5% reducing sugar, all the other are 25% water), 1.65 grams of iron(ic) chloride (FeCl
3) react with the flow inflow reaction zone of 4.1 ml/min with the saccharide solution of 70.62 grams of N,N-DIMETHYLACETAMIDEs (DMAc).Complete charging in the 23rd minute.Now, the temperature of boiling district is 122 ℃, and the temperature of reaction zone is 118 ℃, and the tower top temperature of dehydration rectification zone is 115 ℃.At the 60th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 140 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 58.8 mg/ml.Calculating transformation efficiency by fructose residual volume is 100%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 26.45 grams, and the first organic layer is 66.58 grams, and calculating the 5 hydroxymethyl furfural generating is 7.494 grams, and the productive rate of 5 hydroxymethyl furfural is 51.4 % by mole.
[embodiment 15]
The preparation (15) of 5 hydroxymethyl furfural
The octane of 248.26 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, flow into containing the reaction zone of 8.975 grams of DOWEX 50WX8-100 (catalyzer) and react with the flow of 4.1 ml/min with the saccharide solution of 81.122 grams of dimethyl sulfoxide (DMSO) (DMSO) containing 20.077 grams of fructose.Complete charging in the 20th minute.The methyl iso-butyl ketone (MIBK) of 126 grams (MIBK) is flowed into reaction zone by flow with 4.1 ml/min.Now, the temperature of boiling district is 122 ℃, and the temperature of reaction zone is 117 ℃, and the tower top temperature of dehydration rectification zone is 108 ℃.At the 60th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 93 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 73.2 mg/ml.Calculating transformation efficiency by fructose residual volume is 99.9%.The content of separately analyzing 5 hydroxymethyl furfural in the 3rd organic layer take GC is as 0.15 mg/ml, and in the second organic layer, the content of 5 hydroxymethyl furfural is almost equal to zero.The 4th organic layer is through being weighed as 77.09 grams, and the first organic layer is 60.995 grams, and calculating the 5 hydroxymethyl furfural generating is 11.309 grams, and the productive rate of 5 hydroxymethyl furfural is 81 % by mole.
[embodiment 16]
The preparation (16) of 5 hydroxymethyl furfural
The octane of 279 grams is poured into and boiled district's ebuillition of heated.After boiling the temperature and stability of flow of district, reaction zone and dehydration rectification zone, will contain 10.004 grams of glucose, 0.440 gram of chromous chloride (CrCl
2) react with the flow inflow reaction zone of 4.1 ml/min with the saccharide solution of 91.285 grams of N,N-DIMETHYLACETAMIDEs (DMAc).Complete charging in the 22nd minute.Now, the temperature of boiling district is 127 ℃, and the temperature of reaction zone is 124 ℃, and the tower top temperature of dehydration rectification zone is 108 ℃.At the 60th minute stopped reaction.After cooling, the content of analyzing 5 hydroxymethyl furfural in the 4th organic layer take HPLC is as 33.7 mg/ml, and in the first organic layer, the content of 5 hydroxymethyl furfural is 10.1 mg/ml.Calculating transformation efficiency by glucose residual volume is 98.4%.Separately analyze intimate the equalling zero of content of 5 hydroxymethyl furfural in the 3rd organic layer and the second organic layer with GC.The 4th organic layer is through being weighed as 75.24 grams, and the first organic layer is 19.46 grams, and calculating the 5 hydroxymethyl furfural generating is 2.907 grams, and the productive rate of 5 hydroxymethyl furfural is 41.5 % by mole.
Although the present invention with preferred embodiment openly as above, it is not in order to limit the present invention, and any those skilled in the art can do without departing from the spirit and scope of the present invention to change and revise, and therefore protection scope of the present invention is defined by claims.
Claims (11)
1. a device of preparing 5 hydroxymethyl furfural, comprising:
Reaction zone, comprising the first organic layer and the second organic layer, wherein this first organic layer comprises carbohydrate and solvent, this second organic layer comprises solvent compositions, in this first organic layer, this carbohydrate generates 5 hydroxymethyl furfural and water through dehydration reaction, this solvent compositions is extracted to this 5 hydroxymethyl furfural in this second organic layer, wherein said carbohydrate is fructose or high fructose syrups, described solvent is aprotic polar solvent, described solvent compositions be with this first organic layer in solvent difficulty mix, but can with the solvent of water generates minimum azeotrope dot characteristics, have can not with water dissolve each other solvent or its combination of characteristic,
What be connected with this reaction zone boils district, comprising the mixing solutions being formed by this 5 hydroxymethyl furfural and this solvent compositions, forms the first steam and enter this reaction zone after boiling, and this of this reaction zone the second organic layer is back to this and boils district; And
The rectification zone being connected with this reaction zone, comprising water and liquid level, wherein this liquid level comprises this solvent compositions, and the water in this reaction zone and this first steam are mixed to form the second steam and enter this rectification zone, and this liquid level is back to this second organic layer of this reaction zone.
2. the device of preparing 5 hydroxymethyl furfural according to claim 1, wherein this reaction zone is the liquid accumulation area being made up of multiple distillation plates and plate spacing thereof or is made up of the flash tank of one or more tandem gas-to-liquid contact.
3. right to use requires a preparation method for the 5 hydroxymethyl furfural of the device of preparing 5 hydroxymethyl furfural described in 1, comprising:
Prepare saccharide solution, this saccharide solution comprises carbohydrate and solvent;
This saccharide solution is flowed into reaction zone, to form the first organic layer;
Boil solvent compositions boiling in district, enter this reaction zone to form the first steam, form the second organic layer;
In this first organic layer, this carbohydrate generates 5 hydroxymethyl furfural and water through dehydration reaction, and this solvent compositions is extracted to this 5 hydroxymethyl furfural in this second organic layer;
Mix water and this first steam in this reaction zone, enter rectification zone to form the second steam, to form water and liquid level in this rectification zone, wherein this liquid level comprises this solvent compositions;
This liquid level is back to this second organic layer of this reaction zone;
This second organic layer of this reaction zone is back to this and boils district, to boil at this mixing solutions that in district, formation is formed by this 5 hydroxymethyl furfural and this solvent compositions;
Boil in district at this, this mixing solutions is boiled, enter this reaction zone to form this first steam; And
Cooling this boils unevaporated this mixing solutions in district, to be divided into the 3rd organic layer that is rich in this solvent compositions and the 4th organic layer that is rich in 5 hydroxymethyl furfural;
Wherein said carbohydrate is fructose or high fructose syrups, described solvent is aprotic polar solvent, described solvent compositions be with this first organic layer in solvent difficulty mix, but can with the solvent of water generates minimum azeotrope dot characteristics, have can not with water dissolve each other solvent or its combination of characteristic.
4. the preparation method of 5 hydroxymethyl furfural according to claim 3, wherein this solvent compositions comprises alkanes, chlorination alkanes, ester class, ketone, ethers, Benzene Chloride class or its combination.
5. the preparation method of 5 hydroxymethyl furfural according to claim 4, wherein this alkanes comprises the alkanes of carbon number 7～8.
6. the preparation method of 5 hydroxymethyl furfural according to claim 3, wherein the weight percent of this carbohydrate in this saccharide solution is between 1～30 % by weight.
7. the preparation method of 5 hydroxymethyl furfural according to claim 4, wherein in this second organic layer:
When solvent compositions is containing alkanes, while containing chlorination alkanes, the ratio of one or more in chlorination alkanes and ester class, ketone, ethers, Benzene Chloride class is between 1:1～1:0.
8. the preparation method of 5 hydroxymethyl furfural according to claim 4, wherein in this second organic layer:
In the time that solvent compositions contains alkanes, the ratio of one or more in alkanes and ester class, ketone, ethers, Benzene Chloride class, chlorination alkanes is between 1:1～1:0.
9. the preparation method of 5 hydroxymethyl furfural according to claim 4, wherein in this second organic layer:
In the time that solvent compositions contains alkanes, the ratio of one or more in alkanes and ester class, ketone, ethers, Benzene Chloride class, chlorination alkanes is between 1:1～3:1.
10. the preparation method of 5 hydroxymethyl furfural according to claim 3, wherein the temperature of this dehydration reaction is between 80～150 ℃.
The preparation method of 11. 5 hydroxymethyl furfurals according to claim 3, wherein the time of this dehydration reaction is between 10 minutes to 3 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590283A (en) * | 1983-09-14 | 1986-05-20 | Roquette Freres | Process for manufacturing 5-hydroxymethylfurfural |
| WO2007146636A1 (en) * | 2006-06-06 | 2007-12-21 | Wisconsin Alumni Research Foundation | Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor |
| CN101289435A (en) * | 2008-06-05 | 2008-10-22 | 大连理工大学 | Process for preparing 5-hydroxymethyl-furfural |
| CN101367783A (en) * | 2008-10-10 | 2009-02-18 | 中国科学技术大学 | Preparation method of 5-hydroxymethyl furfural |
| CN101801946A (en) * | 2007-07-18 | 2010-08-11 | 阿彻丹尼尔斯米德兰公司 | Method for production of 5-hydroxymethyl-2-furfural from fructose |
-
2010
- 2010-11-10 CN CN201010542328.8A patent/CN102464637B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590283A (en) * | 1983-09-14 | 1986-05-20 | Roquette Freres | Process for manufacturing 5-hydroxymethylfurfural |
| WO2007146636A1 (en) * | 2006-06-06 | 2007-12-21 | Wisconsin Alumni Research Foundation | Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor |
| CN101801946A (en) * | 2007-07-18 | 2010-08-11 | 阿彻丹尼尔斯米德兰公司 | Method for production of 5-hydroxymethyl-2-furfural from fructose |
| CN101289435A (en) * | 2008-06-05 | 2008-10-22 | 大连理工大学 | Process for preparing 5-hydroxymethyl-furfural |
| CN101367783A (en) * | 2008-10-10 | 2009-02-18 | 中国科学技术大学 | Preparation method of 5-hydroxymethyl furfural |
Non-Patent Citations (4)
| Title |
|---|
| B.F.M.Kuster，等.5-hydroxymethylfurfural(HMF) a review focusing on its manufacture.《Food Science & Technology》.2006 |
| B.F.M.Kuster,等.5-hydroxymethylfurfural(HMF), a review focusing on its manufacture.《Food Science & * |
| Technology》.2006,第42卷(第8期),第314-320页. * |
| Yuriy Roman-Leshkov,等.Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose.《Science》.2006,第312卷(第5782期),第1934页表1、第1935页右栏第2段、第1936页图3、右栏末段到1937页. * |
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