CN109535109A - A kind of method that the liquefaction of wood fibre orientation prepares 5 hydroxymethyl furfural - Google Patents

A kind of method that the liquefaction of wood fibre orientation prepares 5 hydroxymethyl furfural Download PDF

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CN109535109A
CN109535109A CN201811477602.0A CN201811477602A CN109535109A CN 109535109 A CN109535109 A CN 109535109A CN 201811477602 A CN201811477602 A CN 201811477602A CN 109535109 A CN109535109 A CN 109535109A
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hydroxymethyl furfural
raw material
furfural
product
catalyst
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王奎
蒋剑春
刘超
卫民
徐俊明
李静
夏海虹
刘朋
叶俊
周铭昊
王霏
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Institute of Chemical Industry of Forest Products of CAF
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Institute of Chemical Industry of Forest Products of CAF
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

The invention proposes the methods that a kind of orientation liquefaction of wood fibre prepares 5 hydroxymethyl furfural, using wood fibre as raw material, first lignocellulose raw material is mixed with homemade solid acid catalyst and polar non-solute/water double solvents, the pretreatment of slurry method is carried out to lignocellulose raw material at room temperature, heating directional catalyzing liquefaction prepares 5 hydroxymethyl furfural；Filtering, solid residue prepare solid acid catalyst, the distillation of filtrate pressure reduction with classification, separation water, target product 5 hydroxymethyl furfural and by-product furfural and levulic acid；Final residue polar non-solute.The present invention is extensive using raw material sources, reproducible wood fibre is raw material, environmentally protective, low in cost.In polar non-solute/water compounded solvents system, target product 5 hydroxymethyl furfural is selectively good, and yield is high, is easily isolated, and solvent for use, catalyst etc. can high efficiente callback utilize, it is environmental-friendly, be suitable for industrialized production.

Description

A kind of method that the liquefaction of wood fibre orientation prepares 5 hydroxymethyl furfural
Technical field
The invention belongs to prepare the technology of 5 hydroxymethyl furfural, especially pulpous state method pretreatment lignocellulose raw material is then fixed The method for preparing 5 hydroxymethyl furfural to liquefaction.
Background technique
In recent years, increasingly with the exhaustion and world wide environmental pollution of fossil petroleum resources non-renewable on the earth Aggravation, people, which increasingly pay close attention to, produces the energy or chemicals using renewable resource to meet the needs of human society.Biomass Rich reserves are a kind of renewable and cheap resources, and biomass resource plays more and more important in progress of human society Effect, it be considered as part substitution the most effective resource of petroleum resources.Wood fibre is a kind of biomass money abundant Source can be converted into liquid fuel and fine chemicals, therefore be considered as the ideal substitute of fossil resource.Before having In the fine chemicals of scape, 5 hydroxymethyl furfural, furfural and levulic acid regard as ten big carbohydrate by U.S. Department of Energy One of derivative chemicals.
5 hydroxymethyl furfural can be polymerize by methylol in molecule and aldehyde radical Liang Ge functional group, hydrolyze, be esterified, Add hydrogen, halogenation, oxidative dehydrogenation and other chemical reactions.Methylol and aldehyde radical in 5 hydroxymethyl furfural molecular structure assign Its good reactivity and functionalized application prospect: intermediate preparation 2,5- dimethyl furan, 2,5- dimethanol be can be used as The high value added products such as furans, 2,5- dioctyl phthalate furans, 2,5- diformyl furans are widely used in organic conductor, doctor The fields such as medicine, plastics, liquid fuel and its additive.Good reactivity makes 5 hydroxymethyl furfural have wide answer With prospect, while it is difficult to also result in its unstable and purification in process of production.Therefore, existing biomass fast pyrogenation It prepares in the techniques such as 5 hydroxymethyl furfural, product yield is lower, purity difference.
To solve the above-mentioned problems, the solvent liquefaction technique with fine selectivity catalyst is selected, mesh is helped to improve The selectivity of product 5 hydroxymethyl furfural is marked, the generation of the side reactions such as reunion is reduced.Daorattanachai, P, van The seminars such as Putten, R.-J and de Souza, R.L select liquid acid catalysis fructose or the grapes such as hydrochloric acid, sulfuric acid and phosphoric acid Syrup solution prepares 5 hydroxymethyl furfural.Due to the good catalytic activity of liquid acid, 5 hydroxymethyl furfural yield is higher.However While high yield, liquid acid causes the generation of many unnecessary side reactions, and be difficult to separate, corrosivity is strong etc. Problem virtually increases additional equipment investment and operating cost.Solid acid catalyst is returned due to its excellent selectivity, easily The advantages such as low with corrosivity are received, receive the extensive concern of researcher: Amberlyst-70, Amberlyst-15, Graphene oxide、ZrO2, MOR zeolite, the solid acid catalysts such as HY zeolite be applied to catalysis glucose or Person's fructose liquefactionization prepares the research of 5 hydroxymethyl furfural.Gallo, J.M.R et al. are existed using Amberlyst-70 catalyst Fructose hydrolysis 30min is catalyzed at 130 DEG C in the mixed system of gamma-valerolactone and water, 5 hydroxymethyl furfural molar yield reaches To 32%；Sampath, G etc. are catalyzed fructose hydrolysis 1h, 5- methylol using Amberlys-15 catalyst at 120 DEG C Furfural molar yield reaches 64%；Smith, R.L etc. use ZrO2Catalyst is catalyzed fructose hydrolysis at 200 DEG C 10min, 5 hydroxymethyl furfural molar yield are 53%.Above-mentioned solid acid catalyst achieves in 5 hydroxymethyl furfural yield Significant catalytic effect, however to be catalyzed lower reaction condition harsher for solid acid catalyst: the reaction time is longer or adaptability to raw material It is not strong, and the yield of 5 hydroxymethyl furfural and the use longevity of catalyst are reduced for the suction-operated of 5 hydroxymethyl furfural Life, while the toxicity of metallic catalyst also affects the application range of 5 hydroxymethyl furfural product.Recently, ionic liquid conduct Catalyst cellulose or hexose hydrolysis prepare 5 hydroxymethyl furfural and attract wide attention, and ionic liquid has excellent Thermal stability, lower saturated vapour pressure, be easily isolated, reaction condition it is mild.Zhang, Z.C etc. select ionic liquid [EMIM] [Cl] is used as catalyst, and catalytic cellulose liquefies 5min under the conditions of 180 DEG C, and 5 hydroxymethyl furfural yield is 29%. However higher process costs and target product the problems such as being difficult to purifies and separates, limit the work of ionic liquid-catalyzed technique Industry application.Existing 5 hydroxymethyl furfural preparation process including above-mentioned catalytic liquefaction technique is primarily present following main Problem:
(1) liquid mineral acid catalytic erosion is big, it is difficult to recycle, high process cost.
(2) Conventional solid acid catalyst catalytic activity is low, and the reaction time is longer, and reaction temperature is higher.
(3) new catalysts such as ionic liquid and supercritical fluid, higher cost, severe reaction conditions.
(4) mostly with cellulose, glucose or fructose are raw material, and cost of material is high, it is difficult to be applied to lignocellulose raw material Conversion in.
Therefore, a kind of reaction system with fine selectivity and catalytic activity, Efficient Conversion lignocellulose raw material are selected Preparing 5 hydroxymethyl furfural is to solve prior art key of problems.
Summary of the invention
It is good, low in cost that the purpose of the present invention is to provide a kind of adaptability to raw material, and pretreatment of raw material is simple and efficient easy behaviour Make, preparation process strong operability, dicyandiamide solution and catalyst are easily recycled and the rate of recovery is high, target product 5- methylol chaff Aldehyde selectivity is high, the method with good industrial applications prospect.
The technical solution of the present invention is as follows: a kind of wood fibre orientation liquefaction prepares the comprehensive utilization side of 5 hydroxymethyl furfural Method first carries out slurry method and pre-processes to obtain containing lignocellulose raw material, double solvents, catalyst using wood fibre as raw material Slurry premixed liquid；It is 5 hydroxymethyl furfural that the stirring heating of slurry premixed liquid, which realizes that wood fibre orientation liquefaction obtains main component, Liquefaction system；After liquefaction system is separated by filtration solid acid catalyst, filtrate further divides isolated humin by washing Equal residues, filtrate gradually separate water, target product 5 hydroxymethyl furfural, by-product furfural and levulinic by vacuum distillation Acid；Final residue polar non-solute；The double solvents is polar non-solute/water composition；The catalyst is The solid acid catalyst of metal chloride or charcoal base carried metal chloride, active constituent is metal chloride.It is a kind of wooden Fiber alignment liquefaction prepares the method for comprehensive utilization of 5 hydroxymethyl furfural, comprising the following steps:
Step 1: the slurry method of lignocellulose raw material pre-processes: by the lignocellulose raw material powder and solid of clean dried After acid catalyst mixing, premixed with slurry is obtained after stirring sufficiently under polar non-solute/water double solvents mixed room temperature Liquid；
Step 2: the orientation of lignocellulose raw material liquefies: the stirring of slurry premixed liquid is warming up to 150~250 DEG C and sufficiently carries out Liquefaction reaction is oriented, after reaction, obtains the liquefaction system that main component is 5 hydroxymethyl furfural, filtering, separation removes solid Body acid catalyst, then filtrate washing, filtering, residues, the filtrate such as point isolated humin are to be separated；
Step 3: 5 hydroxymethyl furfural isolates and purifies: by filtrate carry out classification rotating pressure-decreasing distillation, gradually separate water, Target product 5 hydroxymethyl furfural, by-product furfural and levulic acid, residue are polar non-solute.
The mass ratio of polar non-solute and water is 90:5~90 in double solvents used.
The solid acid catalyst is added in solvent, under stiring after being mixed using active carbon with metal chloride It is heated to reflux, after filtering and sufficiently being washed with above-mentioned solvent, dried for standby；The active carbon be commercial particulate active carbon or The active carbon that the residue isolated in reaction is prepared through phosphoric acid method carbonization-activation, being heated to reflux temperature is 60~120 DEG C.
The solvent is any one of deionized water, anhydrous methanol, dehydrated alcohol, ethyl acetate, carbon tetrachloride, benzene.
Polar non-solute used is sulfolane, gamma-valerolactone, n,N-Dimethylformamide, dimethyl sulfoxide, four Any one in hydrogen furans.
It is the wood fibre of 1:1~30 and double solvents and 1%-10% that the slurry method pretreatment, which is specifically by mass ratio, Solid acid catalyst mix at room temperature after stirring to slurry premixed liquid.
The wood fibre is poplar, willow, birch, Eucalyptus, China fir, beech, pine, bamboo, rice straw, straw, cotton Any in stalk or corn stover.
The active constituent metal chloride be sodium chloride, aluminium chloride, calcium chloride, zinc chloride, iron chloride, stannic chloride, Any one of magnesium chloride, potassium chloride, lead chloride, copper chloride.
Polar non-solute used in reaction and solid acid catalyst recycle and reuse, and solid residue is used for Prepare solid acid catalyst.
The utility model has the advantages that
1, the method for the present invention first passes through using wood fibre as raw material and carries out the pretreatment of slurry method to lignocellulose raw material, obtain To the slurry premixed liquid containing lignocellulose raw material, solid acid catalyst and double solvents；Resulting slurry premixed liquid is shifted It is catalyzed lower hydrolysis to compressive reaction kettle, target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid is made；It crosses The filter cake obtained after filter is humin, can be used for preparing based solid acid catalyst；Filtrate is separated by vacuum distillation classification, by Step separation water, target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid；Final residue aprotic, polar is molten Agent can be recycled with isolated water is classified.Lignocellulose raw material is from a wealth of sources, low in cost, pretreatment of raw material It is simple and efficient easy to operate, target product 5 hydroxymethyl furfural is selectively good, and commercial viability is strong.
2, the method for the present invention does not have particular/special requirement to lignocellulose raw material, is adaptable to the wooden fibre of various raw material sources Dimension, such as: wood fibre is willow, poplar, Eucalyptus, birch, beech, China fir, bamboo, pine, straw, rice straw, cotton stalk and jade Rice stalk etc..Raw material sources are extensive, greatly reduce the industrial cost of 5 hydroxymethyl furfural.
3, the method for the present invention process operability is strong, and solvent for use sulfolane boiling point is high, and saturated vapor forces down, thermostabilization Property and chemical stability it is excellent, it is good to the selectivity of target product 5 hydroxymethyl furfural, can be high by being simply evaporated under reduced pressure Effect separation target product 5 hydroxymethyl furfural and by-product furfural, levulic acid etc..
4, the method for the present invention solvent for use and catalyst can high efficiente callback, reuse, it is environmental-friendly.
5, the method for the present invention carries out the pretreatment of pulpous state method to lignocellulose raw material, under mild reaction conditions, to wooden Fibrous raw material is pre-processed, easy to operate and efficient.
6, the solid acid catalyst carrier that the method for the present invention uses also may be from humin in reaction process from purchase, Can high efficiente callback reuse, realize lignocellulose raw material comprehensive utilization while reduce process costs.
Detailed description of the invention
Fig. 1 is the nitrogen adsorption desorption curve of the solid acid catalyst of activated carbon supported metal halide, is shown prepared Carbon-based solid acid catalyst there is the cellular structure that is evenly distributed, average pore size is about 3.8nm, is mesoporous catalyst.
Fig. 2 is GC the and HPLC spectrogram of each product standard sample in liquefaction products composition, and upper figure is HPLC spectrogram, and the following figure is GC spectrogram, wherein a is glucose, and b is laevoglucose glycosides, and c is formic acid, and d is levulic acid, and e is sulfolane, and f is left-handed Portugal Grape saccharon, g are 5 hydroxymethyl furfural, and h is furfural.
Fig. 3 is the flow chart for the method that the present invention prepares 5 hydroxymethyl furfural with wood fibre.
Specific embodiment
Present invention is further described in detail with reference to the accompanying drawing.
The method that the present invention prepares 5 hydroxymethyl furfural by orienting liquefaction as raw material using wood fibre, as shown in figure 3, Using wood fibre as raw material, the pretreatment of slurry method first is carried out to lignocellulose raw material, is obtained containing lignocellulose raw material, solid The slurry premixed liquid of acid catalyst and double solvents；Slurry premixed liquid obtained is oriented into liquefaction at a certain temperature, mesh is made Mark product 5 hydroxymethyl furfural and a small amount of by-product furfural, levulic acid etc..After residual reaction liquid is filtered, it is rich in humin Residue it is recyclable prepare solid acid catalyst, filtrate gradually separates water, target product 5 hydroxymethyl furfural through being evaporated under reduced pressure, A small amount of by-product furfural and levulic acid, remaining polar non-solute agent can weigh after mixing in proportion with isolated water It is multiple to use.Lignocellulose raw material is from a wealth of sources, low in cost, and 5 hydroxymethyl furfural is selectively good, and technique is environmentally protective, used Solvent and catalyst can high efficiente callback, reuse.
A kind of wood fibre orientation liquefaction prepares the method for comprehensive utilization of levulic acid, more specific step are as follows:
Step 1: the pretreatment of lignocellulose raw material: it is dry after first cleaning lignocellulose raw material, then pass through high speed Pulverizer is crushed to 200 mesh or so, is 1:1~1:30 lignocellulose raw material powder and double solvents and quality point by mass ratio Number 1%-10% solid acid catalysts mixing is placed in premix kettle, is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: by the granular activated carbon bought (or by reaction residues through phosphoric acid method carbonization-activation Prepare active carbon) it is placed in three-necked flask, by metal chloride (sodium chloride, aluminium chloride, calcium chloride, zinc chloride, iron chloride, chlorination Tin, magnesium chloride, potassium chloride, lead chloride, any in copper chloride) be dissolved in solvent (deionized water, anhydrous methanol, dehydrated alcohol, Ethyl acetate, carbon tetrachloride, any in benzene) in be subsequently poured into three-necked flask, be heated to 60~120 DEG C under stiring and return 0.1~1.5h is flowed, filter and is sufficiently cleaned with above-mentioned solvent after gained filter cake vacuum drying for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, stirring is warming up to 150~ 250 DEG C, react 0.5~3h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.Filtrate In include target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.
Step 4: the separation of 5 hydroxymethyl furfural: putting the filtrate into rectifier unit, under vacuum condition, vacuum degree can be selected - 0.1MPa~-0.01MPa is selected, revolving is gradually heated up and is warming up to 40~70 DEG C, distills 0.1~0.5h, in reclaim liquid phase product Moisture.After no water droplet distillates, 75~110 DEG C are continuously heating to, distills 0.1~0.5h, collects target product 5- methylol Furfural.After dripless distillates, 115~145 DEG C are continuously heating to, distills 0.1~0.5h, collects product furfural.To dripless After distillating, 150~180 DEG C are continuously heating to, distills 0.1~0.5h, collects product levulic acid.It, will after dripless distillates Raffinate standing filters after being cooled to room temperature, and filtrate is reusable as recovered solvent.
All solvents and catalyst used are recyclable, reuse.
Catalyst: solid acid catalyst is laboratory self-control.
Solvent: polar non-solute, technical grade, deionized water.
Above-mentioned reaction process is illustrated with embodiment below.
Embodiment 1:
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material willow, Then 200 mesh or so are crushed to by high speed disintegrator, are that 1:1 lignocellulose raw material powder and sulfolane/water are multiple by mass ratio Bonding solvent (its sulfolan is 90:10 with water quality ratio) is mixed with 1% solid acid catalyst of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, stannic chloride is dissolved in molten It is subsequently poured into three-necked flask in agent deionized water, is heated to 120 DEG C of reflux 0.1h under magnetic stirring, filtered and with above-mentioned Solvent sufficiently cleans after gained filter cake vacuum drying for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 160 DEG C, React 0.5h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include mesh in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc. are marked, it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 50.1% in liquid-phase system, and furfural molar yield is 19.4%, levulic acid mole Yield is 10.0%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.1h, the moisture in reclaim liquid phase product to 40 DEG C.After no water droplet distillates, 75 DEG C are continuously heating to, is steamed 0.1h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 115 DEG C are continuously heating to, distills 0.1h, is collected Product furfural.After dripless distillates, 150 DEG C are continuously heating to, distills 0.1h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 2:
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, by mass ratio be 1:5 lignocellulose raw material powder and gamma-valerolactone/ Water compounded solvents (its sulfolan with water quality ratio be 90:10) mixed with 10% solid acid catalyst of mass fraction be placed in it is pre- In mixed kettle, stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, zinc chloride is dissolved in molten It is subsequently poured into three-necked flask in agent anhydrous methanol, is heated to 70 DEG C of reflux 0.2h under magnetic stirring, filtered and with above-mentioned molten Agent is sufficiently cleaned after gained filter cake vacuum drying for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 180 DEG C, React 1h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It is analyzed through GC and HPLC through GC and HPLC As a result it is found that 5 hydroxymethyl furfural molar yield is 35.1% in liquid-phase system, furfural molar yield is 15.4%, levulinic Sour molar yield is 12.0%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.02MPa vacuum condition, gradually plus Heat revolving distills 0.2h, the moisture in reclaim liquid phase product to 50 DEG C.After no water droplet distillates, 85 DEG C are continuously heating to, is steamed 0.2h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 125 DEG C are continuously heating to, distills 0.2h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.2h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 3:
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:10 lignocellulose raw material powder and N, N- dimethyl by mass ratio Formamide/water double solvents (its sulfolan is 90:30 with water quality ratio) is mixed with 5% solid acid catalyst of mass fraction It is placed in premix kettle, is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, magnesium chloride is dissolved in molten It is subsequently poured into three-necked flask in agent dehydrated alcohol, is heated to 80 DEG C of reflux 0.3h under magnetic stirring, filtered and with above-mentioned molten Agent is sufficiently cleaned after gained filter cake vacuum drying for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 1.5h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include mesh in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc. are marked, it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 45.1% in liquid-phase system, and furfural molar yield is 16.4%, levulic acid mole Yield is 13.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.03MPa vacuum condition, gradually plus Heat revolving distills 0.3h, the moisture in reclaim liquid phase product to 70 DEG C.After no water droplet distillates, 85 DEG C are continuously heating to, is steamed 0.3h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 135 DEG C are continuously heating to, distills 0.3h, is collected Product furfural.After dripless distillates, 165 DEG C are continuously heating to, distills 0.3h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 4:
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are that 1:15 lignocellulose raw material powder and dimethyl are sub- by mass ratio Sulfone/water compounded solvents (its sulfolan is 90:40 with water quality ratio) is mixed with 2% solid acid catalyst of mass fraction to be placed in It premixes in kettle, is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, sodium chloride is dissolved in molten It is subsequently poured into three-necked flask in agent ethyl acetate, is heated to 90 DEG C of reflux 0.4h under magnetic stirring, filtered and with above-mentioned molten Agent is sufficiently cleaned after gained filter cake vacuum drying for use
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 210 DEG C, React 2h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 49.1% in liquid-phase system, and furfural molar yield is 19.4%, levulic acid molar yield It is 9.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.04MPa vacuum condition, gradually plus Heat revolving distills 0.4h, the moisture in reclaim liquid phase product to 40 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.4h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 145 DEG C are continuously heating to, distills 0.4h, is collected Product furfural.After dripless distillates, 175 DEG C are continuously heating to, distills 0.4h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 5:
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are that 1:20 lignocellulose raw material powder and THF/ water are compound by mass ratio Solvent (its sulfolan is 90:50 with water quality ratio) is mixed with 3% solid acid catalyst of mass fraction to be placed in premix kettle, It is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, lead chloride is dissolved in molten It is subsequently poured into three-necked flask in agent carbon tetrachloride, is heated to 100 DEG C of reflux 0.5h under magnetic stirring, filtered and with above-mentioned Solvent sufficiently cleans after gained filter cake vacuum drying for use
Step 3: the hydrolysis of lignocellulose raw material: the hydrolysis of lignocellulose raw material: compressive reaction is added in slurry premixed liquid In kettle, stirring is warming up to 220 DEG C, reacts 3h.After reaction, it filters, filter cake recycles catalyst after washing and drying, to weight It is multiple to use.It is to be separated comprising target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc. in filtrate.Through It is found that 5 hydroxymethyl furfural molar yield is 52.1% in liquid-phase system, furfural molar yield is GC and HPLC analysis result 16.4%, levulic acid molar yield is 7.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.05MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 50 DEG C.After no water droplet distillates, 75 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 125 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 180 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 6:
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are that 1:25 lignocellulose raw material powder and THF/ water are compound by mass ratio Solvent (its sulfolan is 90:60 with water quality ratio) is mixed with 4% solid acid catalyst of mass fraction to be placed in premix kettle, It is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, copper chloride is dissolved in molten It is subsequently poured into three-necked flask in agent benzene, is heated to 110 DEG C of reflux 0.5h under magnetic stirring, filtered and filled with above-mentioned solvent It distinguishes stand-by after washing gained filter cake vacuum drying
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 220 DEG C, React 3h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 52.1% in liquid-phase system, and furfural molar yield is 16.4%, levulic acid molar yield It is 7.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.05MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 50 DEG C.After no water droplet distillates, 75 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 125 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 180 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 7:
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:30 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:70 with water quality ratio) is mixed with 6% solid acid catalyst of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, aluminium chloride is dissolved in molten It is subsequently poured into three-necked flask in agent deionized water, is heated to 120 DEG C of reflux 1.5h under magnetic stirring, filtered and with above-mentioned Solvent sufficiently cleans after gained filter cake vacuum drying for use
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 240 DEG C, React 2h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 43.1% in liquid-phase system, and furfural molar yield is 13.6%, levulic acid molar yield It is 8.8%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.09MPa vacuum condition, gradually plus Heat revolving distills 0.4h, the moisture in reclaim liquid phase product to 70 DEG C.After no water droplet distillates, 110 DEG C are continuously heating to, is steamed 0.4h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 145 DEG C are continuously heating to, distills 0.4h, is collected Product furfural.After dripless distillates, 180 DEG C are continuously heating to, distills 0.4h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 8:
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are that 1:6 lignocellulose raw material powder and sulfolane/water are multiple by mass ratio Bonding solvent (its sulfolan is 90:70 with water quality ratio) is mixed with 7% solid acid catalyst of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, calcium chloride is dissolved in molten It is subsequently poured into three-necked flask in agent dehydrated alcohol, is heated to 80 DEG C of reflux 0.5h under magnetic stirring, filtered and with above-mentioned molten Agent is sufficiently cleaned after gained filter cake vacuum drying for use
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 250 DEG C, React 2h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 47.8% in liquid-phase system, and furfural molar yield is 28.1%, levulic acid molar yield It is 13.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 9:
The present embodiment solvent for use and catalyst are recovered solvent and catalyst in embodiment 8.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:30 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:80 with water quality ratio) is mixed with 8% solid acid catalyst of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, iron chloride is dissolved in molten It is subsequently poured into three-necked flask in agent ethyl acetate, is heated to 80 DEG C of reflux 0.5h under magnetic stirring, filtered and with above-mentioned molten Agent is sufficiently cleaned after gained filter cake vacuum drying for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 50.8% in liquid-phase system, and furfural molar yield is 18.1%, levulic acid molar yield It is 7.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 10:
The present embodiment solvent for use and catalyst are recovered solvent and catalyst in embodiment 9.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:90 with water quality ratio) is mixed with 9% solid acid catalyst of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, potassium chloride is dissolved in molten It is subsequently poured into three-necked flask in agent dehydrated alcohol, is heated to 80 DEG C of reflux 0.5h under magnetic stirring, filtered and with above-mentioned molten Agent is sufficiently cleaned after gained filter cake vacuum drying for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 30.8% in liquid-phase system, and furfural molar yield is 11.1%, levulic acid molar yield It is 7.7%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 11:
The present embodiment solvent for use and catalyst are recovered solvent and catalyst in embodiment 10.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:90 with water quality ratio) is mixed with 10% solid acid catalyst of mass fraction is placed in premix In kettle, stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, stannic chloride is dissolved in molten It is subsequently poured into three-necked flask in agent dehydrated alcohol, is heated to 80 DEG C of reflux 0.5h under magnetic stirring, filtered and with above-mentioned molten Agent is sufficiently cleaned after gained filter cake vacuum drying for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 180 DEG C, React 1h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 37.8% in liquid-phase system, and furfural molar yield is 18.1%, levulic acid molar yield It is 23.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 12:
The present embodiment solvent for use and catalyst are recovered solvent and catalyst in embodiment 11.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material bamboo, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 1% solid acid catalyst of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: the granular activated carbon bought being placed in three-necked flask, sodium chloride is dissolved in molten It is subsequently poured into three-necked flask in agent dehydrated alcohol, is heated to 80 DEG C of reflux 0.5h under magnetic stirring, filtered and with above-mentioned molten Agent is sufficiently cleaned after gained filter cake vacuum drying for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 47.9% in liquid-phase system, and furfural molar yield is 28.1%, levulic acid molar yield It is 12.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 13:
The present embodiment solvent for use is recovered solvent in embodiment 12, and catalyst is that reaction residues are made in embodiment 12 Standby solid acid catalyst.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material willow, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 1% solid acid catalyst of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: by the active carbon that reaction residues are prepared through phosphoric acid method carbonization-activation in embodiment 12 It is placed in three-necked flask, stannic chloride is dissolved in solvent absolute ethyl alcohol and is subsequently poured into three-necked flask, is heated under magnetic stirring 120 DEG C of reflux 0.5h are filtered and are sufficiently cleaned after gained filter cake vacuum drying with above-mentioned solvent for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 46.1% in liquid-phase system, and furfural molar yield is 16.4%, levulic acid molar yield It is 11.7%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.1h, the moisture in reclaim liquid phase product to 40 DEG C.After no water droplet distillates, 75 DEG C are continuously heating to, is steamed 0.1h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 115 DEG C are continuously heating to, distills 0.1h, is collected Product furfural.After dripless distillates, 150 DEG C are continuously heating to, distills 0.1h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 14:
The present embodiment solvent for use is recovered solvent in embodiment 13, and catalyst is that reaction residues are made in embodiment 13 Standby solid acid catalyst.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material willow, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 1% solid acid catalyst of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the preparation of solid acid: by the active carbon that reaction residues are prepared through phosphoric acid method carbonization-activation in embodiment 13 It is placed in three-necked flask, stannic chloride is dissolved in solvent absolute ethyl alcohol and is subsequently poured into three-necked flask, is heated under magnetic stirring 120 DEG C of reflux 0.5h are filtered and are sufficiently cleaned after gained filter cake vacuum drying with above-mentioned solvent for use.
Step 3: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycles catalyst after washing and drying, wait reuse.It include target in filtrate Product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.Through GC and HPLC analysis result it is found that 5 hydroxymethyl furfural molar yield is 42.1% in liquid-phase system, and furfural molar yield is 15.4%, levulic acid molar yield It is 13.9%；
Step 4: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.1h, the moisture in reclaim liquid phase product to 40 DEG C.After no water droplet distillates, 75 DEG C are continuously heating to, is steamed 0.1h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 115 DEG C are continuously heating to, distills 0.1h, is collected Product furfural.After dripless distillates, 150 DEG C are continuously heating to, distills 0.1h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable as recovered solvent.
Embodiment 15:
The present embodiment used catalyst is stannic chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 10% stannic chloride of mass fraction to be placed in premix kettle, room The lower stirring of temperature is to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 69.4% in liquid-phase system, and furfural molar yield is 22.3%, levulic acid mole Yield is 10.9%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 16:
The present embodiment used catalyst is aluminium chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 10% aluminium chloride of mass fraction to be placed in premix kettle, room The lower stirring of temperature is to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 59.4% in liquid-phase system, and furfural molar yield is 12.3%, levulic acid mole Yield is 18.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 17:
The present embodiment used catalyst is zinc chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 10% zinc chloride of mass fraction to be placed in premix kettle, room The lower stirring of temperature is to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 39.4% in liquid-phase system, and furfural molar yield is 22.3%, levulic acid mole Yield is 20.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 18:
The present embodiment used catalyst is sodium chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 10% sodium chloride of mass fraction to be placed in premix kettle, room The lower stirring of temperature is to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 49.4% in liquid-phase system, and furfural molar yield is 12.3%, levulic acid mole Yield is 12.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 19:
The present embodiment used catalyst is calcium chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 10% calcium chloride of mass fraction to be placed in premix kettle, room The lower stirring of temperature is to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 55.4% in liquid-phase system, and furfural molar yield is 19.9%, levulic acid mole Yield is 16.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 20:
The present embodiment used catalyst is iron chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are 1:20 lignocellulose raw material powder and sulfolane/water by mass ratio Double solvents (its sulfolan is 90:10 with water quality ratio) is mixed with 10% iron chloride of mass fraction to be placed in premix kettle, room The lower stirring of temperature is to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 65.4% in liquid-phase system, and furfural molar yield is 30.9%, levulic acid mole Yield is 22.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 21:
The present embodiment used catalyst is magnesium chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are that 1:10 lignocellulose raw material powder and THF/ water are compound by mass ratio Solvent (its sulfolan is 90:90 with water quality ratio) is mixed with 5% magnesium chloride of mass fraction to be placed in premix kettle, at room temperature Stirring is to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 66.4% in liquid-phase system, and furfural molar yield is 14.9%, levulic acid mole Yield is 12.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 22:
The present embodiment used catalyst is potassium chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, are that 1:10 lignocellulose raw material powder and dimethyl are sub- by mass ratio Sulfone/water compounded solvents (its sulfolan is 90:90 with water quality ratio) is mixed with 5% magnesium chloride of mass fraction is placed in premix kettle In, it is stirred at room temperature to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 70.4% in liquid-phase system, and furfural molar yield is 24.9%, levulic acid mole Yield is 12.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 23:
The present embodiment used catalyst is lead chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, by mass ratio be 1:20 lignocellulose raw material powder and gamma-valerolactone/ Water compounded solvents (its sulfolan is 90:90 with water quality ratio) are mixed with 5% lead chloride of mass fraction to be placed in premix kettle, It is stirred at room temperature to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 60.4% in liquid-phase system, and furfural molar yield is 14.9%, levulic acid mole Yield is 12.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.
Embodiment 24:
The present embodiment used catalyst is copper chloride.
Step 1: the pretreatment of lignocellulose raw material: it is dry after being first washed with deionized water lignocellulose raw material poplar, Then 200 mesh or so are crushed to by high speed disintegrator, by mass ratio be 1:20 lignocellulose raw material powder and gamma-valerolactone/ Water compounded solvents (its sulfolan is 90:90 with water quality ratio) are mixed with 5% copper chloride of mass fraction to be placed in premix kettle, It is stirred at room temperature to slurry, for use.
Step 2: the hydrolysis of lignocellulose raw material: slurry premixed liquid is added in compressive reaction kettle, and stirring is warming up to 200 DEG C, React 2h.After reaction, it filters, filter cake recycling after washing and drying prepares active carbon, wait reuse.Include in filtrate Target product 5 hydroxymethyl furfural and a small amount of by-product furfural and levulic acid etc., it is to be separated.It can through GC and HPLC analysis result Know, 5 hydroxymethyl furfural molar yield is 69.4% in liquid-phase system, and furfural molar yield is 15.9%, levulic acid mole Yield is 13.8%；
Step 3: the separation of 5 hydroxymethyl furfural: put the filtrate into rectifier unit, -0.1MPa vacuum condition, gradually plus Heat revolving distills 0.5h, the moisture in reclaim liquid phase product to 60 DEG C.After no water droplet distillates, 80 DEG C are continuously heating to, is steamed 0.5h is evaporated, target product 5 hydroxymethyl furfural is collected.After dripless distillates, 120 DEG C are continuously heating to, distills 0.5h, is collected Product furfural.After dripless distillates, 160 DEG C are continuously heating to, distills 0.5h, collects product levulic acid.It is evaporated to dripless After out, filtered after raffinate standing is cooled to room temperature, filtrate is reusable with catalyst as recovered solvent.

Claims (10)

1. the method for comprehensive utilization that a kind of wood fibre orientation liquefaction prepares 5 hydroxymethyl furfural, which is characterized in that with wooden fibre Dimension is raw material, first carry out slurry method pre-process to obtain containing lignocellulose raw material, double solvents, catalyst slurry premixed liquid； The stirring heating of slurry premixed liquid realizes that wood fibre orientation liquefaction obtains the liquefaction system that main component is 5 hydroxymethyl furfural；Liquid After change system is separated by filtration solid acid catalyst, filtrate further divides isolated humin residue by washing, and filtrate passes through Vacuum distillation gradually separates water, target product 5 hydroxymethyl furfural, by-product furfural and levulic acid；Final residue polarity is non- Proton solvent；The double solvents is polar non-solute/water composition；The catalyst is metal chloride or charcoal base The solid acid catalyst of carried metal chloride, active constituent are metal chloride.
2. wood fibre orientation liquefaction according to claim 1 prepares the method for comprehensive utilization of 5 hydroxymethyl furfural, special Sign is, comprising the following steps:
Step 1: the slurry method of lignocellulose raw material pre-processes: lignocellulose raw material powder and the solid acid of clean dried are urged Agent mixing after, under polar non-solute/water double solvents mixed room temperature stir sufficiently after obtain slurry premixed liquid；
Step 2: the orientation of lignocellulose raw material liquefies: the stirring of slurry premixed liquid is warming up to 150~250 DEG C and is sufficiently oriented Liquefaction reaction obtains the liquefaction system that main component is 5 hydroxymethyl furfural, filtering, separation removal solid acid after reaction Catalyst, then filtrate washing, filtering, point isolated humin residue, filtrate are to be separated；
Step 3: 5 hydroxymethyl furfural isolates and purifies: filtrate being carried out classification rotating pressure-decreasing distillation, gradually separates water, target Product 5 hydroxymethyl furfural, by-product furfural and levulic acid, residue are polar non-solute.
3. wood fibre orientation liquefaction according to claim 1 or 2 prepares the method for comprehensive utilization of 5 hydroxymethyl furfural, Be characterized in that: the mass ratio of polar non-solute and water is 90:5~90 in double solvents used.
4. wood fibre orientation liquefaction according to claim 1 or 2 prepares the method for comprehensive utilization of 5 hydroxymethyl furfural, Be characterized in that: the solid acid catalyst is added in solvent, under stiring after being mixed using active carbon with metal chloride It is heated to reflux, after filtering and sufficiently being washed with above-mentioned solvent, dried for standby；The active carbon is for commercial particulate active carbon or instead The active carbon that the residue isolated in answering is prepared through phosphoric acid method carbonization-activation, being heated to reflux temperature is 60~120 DEG C.
5. wood fibre orientation liquefaction according to claim 4 prepares the method for comprehensive utilization of 5 hydroxymethyl furfural, special Sign is: the solvent is any one of deionized water, anhydrous methanol, dehydrated alcohol, ethyl acetate, carbon tetrachloride, benzene.
6. wood fibre orientation liquefaction according to claim 1 or 2 prepares the method for comprehensive utilization of 5 hydroxymethyl furfural, Be characterized in that: polar non-solute used is sulfolane, gamma-valerolactone, n,N-Dimethylformamide, dimethyl sulfoxide, four Any one in hydrogen furans.
7. wood fibre orientation liquefaction according to claim 1 or 2 prepares the method for comprehensive utilization of 5 hydroxymethyl furfural, Be characterized in that: it is the wood fibre of 1:1~30 and double solvents and 1wt%- that the slurry method pretreatment, which is specifically by mass ratio, The solid acid catalyst of 10wt% stirs after mixing at room temperature to slurry premixed liquid.
8. the method that wood fibre orientation liquefaction according to claim 1 or 2 prepares 5 hydroxymethyl furfural, feature exist In: the wood fibre is poplar, willow, birch, Eucalyptus, China fir, beech, pine, bamboo, rice straw, straw, cotton stalk or jade Any in rice stalk.
9. the method that wood fibre orientation liquefaction according to claim 1 or 2 prepares 5 hydroxymethyl furfural, feature exist In: the active constituent metal chloride is sodium chloride, aluminium chloride, calcium chloride, zinc chloride, iron chloride, stannic chloride, chlorination Any one of magnesium, potassium chloride, lead chloride, copper chloride.
10. the method that wood fibre orientation liquefaction according to claim 1 or 2 prepares 5 hydroxymethyl furfural, feature exist In: polar non-solute used in reaction and solid acid catalyst recycle and reuse, and solid residue is used to prepare Solid acid catalyst.
CN201811477602.0A 2018-12-05 2018-12-05 A kind of method that the liquefaction of wood fibre orientation prepares 5 hydroxymethyl furfural Pending CN109535109A (en)

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Application publication date: 20190329