CN108114746A - A kind of preparation method and application of lignin-base acidic catalyst - Google Patents
A kind of preparation method and application of lignin-base acidic catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and application of lignin-base acidic catalyst, which is：First, carbon dioxide dry ice prepares the lignin of carboxylic acid functional under mechanical energy effect, then, the lignin of carboxylic acid functional is further acidified under the action of an acid, catalyst of the lignin-base containing carboxylic acid functional is applied to the hydrolysis of the carbohydrate polymer in lignocellulose-like biomass, obtains high monose yield.The preparation method of catalyst of the lignin-base containing carboxylic acid functional is simple in this method, and the lignin of one of raw material derives from a wealth of sources, and coordinates ultralow acid solution that can obtain very high carbohydrate polymer conversion ratio and monose yield.
Description
Technical field
The present invention relates to the agricultural-forestry biomass utilization of resources and processing technology fields, and in particular to a kind of lignin-base acidity is urged
The preparation method and application of agent.
Background technology
China's biomass resource very abundant, Bio-energy Development not only can largely alleviate energy scarcity
Situation can also mitigate environmental pollution caused by combustion of fossil fuel.Lignocellulosic is mainly by cellulose, hemicellulose and wood
Quality forms, and wherein cellulose and hemicellulose become fermentable carbohydrate after hydrolysis, and fermentable sugars is in enzyme catalysis
Under change into fuel alcohol.Biomass by hydrolyzation is the key that convert biomass into useful carbohydrate and platform chemicals.Biology
The method for hydrolysis of matter is primarily referred to as the methods of sour water solution, enzyme hydrolysis and high temperature liquid water hydrolyze.Enzyme hydrolysis and high temperature liquid water
Hydrolysis is still within the experimental study stage at present due to cost and technology etc..
For a long time, sour water solution can be divided into Concentrated acid hydrolysis, dilute acid hydrolysis and extremely low acids hydrolysis to acid-hydrolyzed historical origin.Concentrated acid water
Solution refers to sulfuric acid or hydrochloric acid method by biomass by hydrolyzation into monose of the concentration more than 30%.Low energy consumption for Concentrated acid hydrolysis, because it
(such as 20 DEG C -50 DEG C) and the pressure of 1 normal atmosphere can carry out catalytic reaction at low temperature.The rate of recovery of sugar is high, it is recyclable about
90% cellulose, sugar [Hamelinck C N, Hooijdonk V H G, the Faaij AP of hemicellulose conversion
C.Biomass and Bioenergy,2005,28:384-410.].But Concentrated acid hydrolysis process has sternly the water content of raw material
The requirement of lattice.It is using Concentrated acid hydrolysis cellulose meeting corrosion experiment equipment, it is necessary to rotten using resistance to strong acid in addition to the requirement of water content
Corrosion material, this considerably increases the costs of equipment and materials.And a large amount of high concentrated acid waste liquor contamination environment, recycling compared with
Difficulty adds the cost of Concentrated acid hydrolysis from raw material, these all constrain the further development of Concentrated acid hydrolysis.
It is catalyst by cellulose, hemicellulose that dilute acid hydrolysis, which refers generally to inorganic acids such as the sulfuric acid within 10% or hydrochloric acid,
The method of monose, 100-240 DEG C of temperature are hydrolyzed into, pressure is more than hold-up vapour pressure [W.Korbitz.Renewable
Enegry,1999,16:1078-1083].Dilute acid hydrolysis carries out at high temperature under high pressure, several seconds of reaction time or a few minutes.
Such as stopped more than ten seconds in 237 DEG C, 1% dilute sulfuric acid environment, cellulosic material by discharge more than 50% sugar.But essence
On, most dilute acid hydrolysis is limited in sugar yield 50% or so.This is because there are two types of reactions during this.It is once fine
The plain molecule of dimension is converted into sugar, and then sugar is just converted into the chemical substances such as furfural by second reaction, causes the yield drop of sugar
It is low, and the degradation products such as furfural are also to microbial fermentation toxic side effect.That is, the temperature of dilute acid hydrolysis is higher, item is reacted
Part is stronger, and the monose obtained in hydrolytic process can further degrade generation to harmful byproduct that ferments.
Extremely low acids hydrolysis (extremely low sulfuric acid, ELA, acid concentration 0.1% within) becomes in recent years
Research hotspot, reaction temperature usually at 200 DEG C or more, acid concentration using it is more be that mass fraction is 0.05%-0.1%
Hydrochloric acid or sulfuric acid.Ultralow acid is low to the corrosivity of equipment, reduces the subsequent processing amount of acid, is reducing environmental pollution and reducing life
More other techniques have larger advantage in terms of production cost.
Because above advantage, extremely low acids hydrolysis is subject to more and more focus of attention.
It is mainly liquid acid hydrolysis process above, and solid acid hydrolysis hydrolyze compared with liquid acid and easily realize serialization, production
The advantages that object and catalyst are easily separated, catalyst is small to equipment corrosion, and solid acid catalyst is recyclable.In emerging biomass by hydrolyzation
Aspect, heteropoly acid, load-SO3The agraphitic carbon of H/-COOH/-OH groups, the activated carbon of sulfonation, sulfonate resin, ion exchange
The solid acids such as resin, stratiform transition metal oxide, metal phosphate and zeolite molecular sieve obtain extensively using and obtain compared with
High catalytic effect.
The content of the invention
The purpose of the present invention is be directed to lignocellulose biomass concentrated acid and dilute acid hydrolysis existing strong acid, condition in the process
The problems such as harsh, experiment container requirement height, hydrolysising by-product are mostly and waste liquid is difficult, provides a kind of lignin-base containing carboxylic acid
The preparation method of the catalyst of functional group, and applied to the carbohydrate polymer in hydrolysis of lignocellulose biomass.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of lignin-base acidic catalyst, this method is by lignin and carbon dioxide dry ice in mechanical energy
It is prepared under effect, is specially：By lignin and dry ice according to 1:1~100 mass ratio mixing, ball milling or sledge mill, then
Further acidification is carried out to the lignin after above-mentioned ball milling with acid solution, is then washed, it is dry to get to final wooden
Catalyst of the plain base containing carboxylic acid functional.
The lignin is：Cloth Louth (Brauns) native lignin (BNL), Nuo De (Nard) lignin, Beckman
(Bjorkman) lignin (MWL), cellulolytic enzyme lignin (CEL), ethanol lignin, dioxane lignin, coloured glaze guanidine-acetic acid lignin,
Phenol-lignin, lignosulphonic acid, alkali lignin, sulfidated lignin, chlorinated lignin, proflavine sulfate (Klason lignins), hydrochloric acid lignin, cuprammonium wood
One or more of element, periodates lignin.
The acid solution is the mixing of inorganic acid solution, organic acid soln or the two, and the concentration of the acid solution is：
0.5-1.5M, acidificatoin time for 10 minutes -24 it is small when.
The acid solution is hydrochloric acid solution, sulfuric acid solution, salpeter solution, phosphoric acid solution, in trifluoromethanesulfonic acid solution
It is one or several kinds of.
The rotating speed of ball milling is：100-650 turns/min, and Ball-milling Time is：10 minutes~96 it is small when.
A kind of application of lignin-base acidic catalyst, the lignin-base acidic catalyst are used for hydrolysis of lignocellulose,
Specifically follow the steps below：First by lignin-base acidic catalyst and pretreated lignocellulose biomass according to
Mass ratio 1：100~1：1 ratio is put on ball mill, and ball milling is carried out under the rotating speed of 100-650 turns/min, and the time is 10 points
When clock~96 are small；Then the mixture after ball milling is transferred in ultralow acid solution, in the range of temperature is 120~225 DEG C, instead
1~480min is answered, the solution based on reduced sugar is obtained, supernatant is taken after separation.
The lignocellulose biomass is agricultural residue, timber and forest residue, algae, kudzu, coal, grass
This energy crop, lignocellulose biomass, plant biomass or its mixture.
The preferred maize straw of the agricultural residue, straw, bagasse, rice husk or rice straw；The timber and forest are residual
Excess, preferably pine tree, willow, pesudotsuga taxifolia, Oak Tree, sawdust, paper/paper pulp discarded object or wood-fibred；The draft energy crop,
It is preferred that switchgrass, reed canary grass or Chinese silvergrass；The lignocellulose biomass, preferably lignin, cellulose and hemicellulose.
The ultralow acid is the organic acid soln or inorganic acid solution or the two that mass concentration is 0.001~0.1%
Mixing, mass concentration of the lignocellulose biomass in ultralow acid solution be 0.1~30%.
The lignocellulose biomass is preprocess method, is specially：Lignocellulose biomass is dried,
Until then water content removes dust, is put in 40 DEG C of baking oven and is dried to sample up to constant weight, then by sample less than 10wt%
It crushes and crosses 40 mesh sieves, drying to constant weight for drying box at 40 DEG C, after the constant weight standard heats 1h again for sample, sample weight
Amount variation is ± 0.1.
Preferably, ultralow acid is aqueous hydrochloric acid solution either aqueous sulfuric acid or the nitre that mass concentration is 0.005~0.1%
One or several kinds in aqueous acid.
Preferably, it is described to be separated into filtering or centrifugation.
The present invention has the following advantages：First, usually source is wide for catalyst of the lignin-base containing carboxylic acid functional its raw material wood
General, preparation process is simple, and compared with liquid acid, lignin-base solid acid catalysis has apparent advantage.Second, the present invention combines
Ultralow acid solution advantage in solid acid and liquid acid is since acid concentration used is extremely low, small to equipment corrosion, right
Environmental pollution is little, is a kind of environmentally friendly technology for hydrolyzing.3rd, catalyst of the lignin-base containing carboxylic acid functional is applied to wooden fibre
Cellulosic biomass hydrolysis is tieed up, mild condition, hydrolysis rate are fast, obtain very high reduced sugar yield.The present invention is from three great achievement of biomass
/ mono- lignin sets out, and produces solid acid catalyst using simple preparation process, is biomass economy good one
A repeats itself.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is from embodiment
Limitation, if the person skilled in the art in the field makes the present invention according to the invention described above content some nonessential improvement
And adjustment, still fall within protection scope of the present invention.
Lignocellulose biomass involved in following all embodiments is all needed by handling as follows：
Lignocellulose biomass is dried, until then water content removes dust, be put in 40 DEG C less than 10wt%
Baking oven in be dried to sample up to constant weight, then by sample comminution and cross 20 mesh sieves, drying to constant weight for drying box at 40 DEG C, described
Constant weight standard heat 1h again for sample after, example weight changes ± 0.1.
Embodiment 1
Contrast experiment：The hydrolysis of cellulose, 215 DEG C, no lignin-base acidic catalyst, the ultralow acid solutions of 0.012wt%
(a) cellulose hydrolysis prepares monose：1g celluloses are put on ball mill first, under the rotating speed of 500 turns/min
Ball milling is carried out, when the time is 2 small, the cellulose 40mg after ball milling is then taken to be transferred in the reaction kettle of 15ml, is put into 4ml's
In the ultralow hydrochloric acid solution of 0.012wt%, 215 DEG C are begun heat to from room temperature, and keeps 10min, rapidly will after reaction
Reaction kettle takes out, and ice water cooling obtains the solution based on reduced sugar to terminate reaction.
(b) reducing sugar analysis：Reduction sugar juice after reaction is diluted, is filtered, what is be obtained by filtration is deposited in 40 DEG C
It weighs after vacuum drying, the conversion ratio of cellulose is 40%.Content of reducing sugar is analyzed using high-efficient liquid phase color law popularization, after measured
Glucose yield is 38%.
Embodiment 2
Contrast experiment：The hydrolysis of cellulose, 215 DEG C, no dry ice synthesis lignin-base acidic catalyst is (from alkali wood
Element), the ultralow acid solutions of 0.012wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is put in smash grinding jar, with 500 turns/
When the rotating speed ball milling 48 of min is small, then with 150ml concentration be 0.1M hydrochloric acid solutions in apparatus,Soxhlet's to above-mentioned ball milling after
Lignin carries out further acidification, then carries out water to obtaining lignin-base acidic catalyst with the water of 10 times of amounts of catalyst
It washes, is put in and is dried in 40 DEG C of vacuum drying oven to get (control is catalyzed to final lignin-base acidic catalyst
Agent).
(b) hydrolysis of cellulose prepares monose：First by 250mg lignin-bases acidic catalyst (control catalyst)
It is put in 1.0g celluloses on ball mill, ball milling is carried out under the rotating speed of 500 turns/min, when the time is 2.0 small, then by ball milling
Cellulose is transferred in 15ml reaction kettles, is put into lignin-base acidic catalyst (control catalyst) 50mg mixtures afterwards
In the ultralow hydrochloric acid solution of the 0.012wt% of 4ml, 215 DEG C are begun heat to from room temperature, and keeps 10min, it is fast after reaction
Speed takes out reaction kettle, and ice water cooling obtains the solution based on reduced sugar to terminate reaction.By the solution based on reduced sugar into
Row centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, and then 40 DEG C of vacuum are done
It is dry, weigh, calculate cellulose conversion ratio be 49% (quality for having deducted solid catalyst).Supernatant is taken to use efficient liquid
Content of reducing sugar is analyzed in the law popularization of phase color, and glucose yield is 45% after measured.
Embodiment 3
The hydrolysis of cellulose：215 DEG C, 10min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.012wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of cellulose prepares monose：First by 250mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g celluloses are put on ball mill, and ball milling is carried out under the rotating speed of 500 turns/min, then will be after ball milling when the time is 2.0 small
Cellulose is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 50mg mixtures in 15ml reaction kettles, is put into 4ml
0.012wt% ultralow hydrochloric acid solution in, begin heat to 215 DEG C from room temperature, and keep 10min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose is 93% (quality for having deducted solid catalyst).Supernatant is taken to use efficient liquid phase
Content of reducing sugar is analyzed in color law popularization, and glucose yield is 89% after measured.
Embodiment 4
The hydrolysis of cellulose：225 DEG C, 10min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.012wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of cellulose prepares monose：First by 250mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g celluloses are put on ball mill, and ball milling is carried out under the rotating speed of 500 turns/min, then will be after ball milling when the time is 2.0 small
Cellulose is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 50mg mixtures in 15ml reaction kettles, is put into 4ml
0.012wt% ultralow hydrochloric acid solution in, begin heat to 225 DEG C from room temperature, and keep 10min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose is 100% (quality for having deducted solid catalyst).Supernatant is taken to use efficient liquid phase
Content of reducing sugar is analyzed in color law popularization, and glucose yield is 96% after measured.
Embodiment 5
The hydrolysis of cellulose：225 DEG C, 10min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
36h), the ultralow acid solutions of 0.012wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 36 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of cellulose prepares monose：First by 250mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g celluloses are put on ball mill, and ball milling is carried out under the rotating speed of 500 turns/min, then will be after ball milling when the time is 2.0 small
Cellulose is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 50mg mixtures in 15ml reaction kettles, is put into 4ml
0.012wt% ultralow hydrochloric acid solution in, begin heat to 225 DEG C from room temperature, and keep 10min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose is 96% (quality for having deducted solid catalyst).Supernatant is taken to use efficient liquid phase
Content of reducing sugar is analyzed in color law popularization, and glucose yield is 90% after measured.
Embodiment 6
The hydrolysis of cellulose：180 DEG C, 240min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.025wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of cellulose prepares monose：First by 250mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g celluloses are put on ball mill, and ball milling is carried out under the rotating speed of 500 turns/min, then will be after ball milling when the time is 2.0 small
Cellulose is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 50mg mixtures in 15ml reaction kettles, is put into 4ml
0.025wt% ultralow hydrochloric acid solution in, begin heat to 180 DEG C from room temperature, and keep 240min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose is 88% (quality for having deducted solid catalyst).Supernatant is taken to use efficient liquid phase
Content of reducing sugar is analyzed in color law popularization, and glucose yield is 83% after measured.
Embodiment 7
The hydrolysis of cellulose：150 DEG C, 360min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.050wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of cellulose prepares monose：First by 250mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g celluloses are put on ball mill, and ball milling is carried out under the rotating speed of 500 turns/min, then will be after ball milling when the time is 2.0 small
Cellulose is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 50mg mixtures in 15ml reaction kettles, is put into 4ml
0.050wt% ultralow hydrochloric acid solution in, begin heat to 150 DEG C from room temperature, and keep 360min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose is 83% (quality for having deducted solid catalyst).Supernatant is taken to use efficient liquid phase
Content of reducing sugar is analyzed in color law popularization, and glucose yield is 80% after measured.
Embodiment 8
The hydrolysis of cellulose：225 DEG C, 10min is kept, lignin-base acidic catalyst is (from ethanol lignin, ball milling
48h), the ultralow acid solutions of 0.012wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Ethanol lignin 1g is mixed with dry ice 20g and is put in smash
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in grinding jar
In further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base
Acidic catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst
Agent.
(b) hydrolysis of cellulose prepares monose：First by 250mg lignin-bases acidic catalyst (deriving from ethanol lignin)
It is put in 1.0g celluloses on ball mill, ball milling is carried out under the rotating speed of 500 turns/min, when the time is 2.0 small, then by ball milling
Cellulose is transferred in 15ml reaction kettles, is put into lignin-base acidic catalyst (deriving from ethanol lignin) 50mg mixtures afterwards
In the ultralow hydrochloric acid solution of the 0.012wt% of 4ml, 225 DEG C are begun heat to from room temperature, and keeps 10min, it is fast after reaction
Speed takes out reaction kettle, and ice water cooling obtains the solution based on reduced sugar to terminate reaction.By the solution based on reduced sugar into
Row centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, and then 40 DEG C of vacuum are done
It is dry, weigh, calculate cellulose conversion ratio be 100% (quality for having deducted solid catalyst).Supernatant is taken using efficient
Content of reducing sugar is analyzed in the law popularization of liquid phase color, and glucose yield is 95% after measured.
Embodiment 9
The hydrolysis of cellulose：190 DEG C, 60min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.005wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of cellulose prepares monose：First by 250mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g celluloses are put on ball mill, and ball milling is carried out under the rotating speed of 500 turns/min, then will be after ball milling when the time is 2.0 small
Cellulose is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 200mg mixtures in 15ml reaction kettles, is put into 4ml
0.005wt% ultralow hydrochloric acid solution in, begin heat to 190 DEG C from room temperature, and keep 60min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose is 80% (quality for having deducted solid catalyst).Supernatant is taken to use efficient liquid phase
Content of reducing sugar is analyzed in color law popularization, and glucose yield is 76% after measured.
Embodiment 10
The hydrolysis of Fast growth poplar：215 DEG C, 10min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.025wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of Fast growth poplar prepares monose：First by 250mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g Fast growth poplars are put on ball mill, and ball milling is carried out under the rotating speed of 500 turns/min, then will be after ball milling when the time is 2.0 small
Fast growth poplar is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 50mg mixtures in 15ml reaction kettles, is put into 4ml
0.025wt% ultralow hydrochloric acid solution in, begin heat to 215 DEG C from room temperature, and keep 10min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose in Fast growth poplar is 80% (quality for having deducted solid catalyst).Supernatant is taken to use
Content of reducing sugar is analyzed in high-efficient liquid phase color law popularization, and glucose yield is 76% after measured.
Embodiment 11
The hydrolysis of eucalyptus barks：180 DEG C, 180min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.050wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of eucalyptus barks prepares monose：First by 250mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g eucalyptus barks are put on ball mill, and ball milling is carried out under the rotating speed of 650 turns/min, then will be after ball milling when the time is 2.0 small
Fast growth poplar is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 50mg mixtures in 15ml reaction kettles, is put into 4ml
0.050wt% ultralow hydrochloric acid solution in, begin heat to 180 DEG C from room temperature, and keep 180min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose in eucalyptus barks is 89% (quality for having deducted solid catalyst).Supernatant is taken to use
Content of reducing sugar is analyzed in high-efficient liquid phase color law popularization, and glucose yield is 85% after measured.
Embodiment 12
The hydrolysis of eucalyptus barks：150 DEG C, 360min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.100wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of eucalyptus barks prepares monose：First by 150mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g eucalyptus barks are put on ball mill, and ball milling is carried out under the rotating speed of 650 turns/min, then will be after ball milling when the time is 2.0 small
Fast growth poplar is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 50mg mixtures in 15ml reaction kettles, is put into 4ml
0.100wt% ultralow hydrochloric acid solution in, begin heat to 150 DEG C from room temperature, and keep 360min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose in eucalyptus barks is 75% (quality for having deducted solid catalyst).Supernatant is taken to use
Content of reducing sugar is analyzed in high-efficient liquid phase color law popularization, and glucose yield is 71% after measured.
Embodiment 13
The hydrolysis of eucalyptus barks：120 DEG C, 480min is kept, lignin-base acidic catalyst is (from alkali lignin, ball milling
48h), the ultralow acid solutions of 0.001wt%
(a) catalyst preparation of the lignin-base containing carboxylic acid functional:Alkali lignin 1g is mixed with dry ice 20g and is put in ball mill
It is then 0.1M hydrochloric acid solutions in apparatus,Soxhlet's with 150ml concentration when small with the rotating speed ball milling 48 of 500 turns/min in tank
Further acidification is carried out to the lignin after above-mentioned ball milling, then with the water of 10 times of amounts of catalyst to obtaining lignin-base acid
Property catalyst is washed, and is put in and is dried in 40 DEG C of vacuum drying oven to get to final lignin-base acidic catalyst.
(b) hydrolysis of eucalyptus barks prepares monose：First by 150mg lignin-bases acidic catalyst (derive from alkali lignin) with
1.0g eucalyptus barks are put on ball mill, and ball milling is carried out under the rotating speed of 650 turns/min, then will be after ball milling when the time is 2.0 small
Fast growth poplar is transferred to lignin-base acidic catalyst (deriving from alkali lignin) 100mg mixtures in 15ml reaction kettles, is put into 4ml
0.001wt% ultralow hydrochloric acid solution in, begin heat to 120 DEG C from room temperature, and keep 480min, after reaction rapidly
Reaction kettle is taken out, ice water cooling obtains the solution based on reduced sugar to terminate reaction.Solution based on reduced sugar is carried out
It centrifuges, 8000 turns/min of centrifugation rate, centrifugation time 8 minutes.Solid portion is washed, then 40 DEG C vacuum drying,
It weighs, the conversion ratio for calculating cellulose in eucalyptus barks is 50% (quality for having deducted solid catalyst).Supernatant is taken to use
Content of reducing sugar is analyzed in high-efficient liquid phase color law popularization, and glucose yield is 45% after measured.
Claims (10)
1. a kind of preparation method of lignin-base acidic catalyst, it is characterised in that this method is by lignin and carbon dioxide dry ice
It is prepared under mechanical energy effect, is specially：By lignin and dry ice according to 1：1~1：100 mass ratio mixing, ball milling or
Then then sledge mill is washed the further acidification of lignin after above-mentioned ball milling with acid solution, dry to get to final
Catalyst of the lignin-base containing carboxylic acid functional.
2. a kind of preparation method of lignin-base acidic catalyst according to claim 1, it is characterised in that described is wooden
Element is：Cloth Louth (Brauns) native lignin (BNL), Nuo De (Nard) lignin, Beckman (Bjorkman) lignin (MWL), fibre
The plain catabolic enzyme lignin (CEL) of dimension, ethanol lignin, dioxane lignin, coloured glaze guanidine-acetic acid lignin, phenol-lignin, lignosulphonic acid, alkali wood
In element, sulfidated lignin, chlorinated lignin, proflavine sulfate (Klason lignins), hydrochloric acid lignin, cuprammonium lignin, periodates lignin
It is one or more of.
A kind of 3. method of the preparation of lignin-base acidic catalyst according to claim 1, it is characterised in that the acid
Solution is the mixing of inorganic acid solution, organic acid soln or the two, and the concentration of the acid solution is：0.5-1.5M, acidificatoin time
For 10 minutes~24 it is small when.
A kind of 4. method of the preparation of lignin-base acidic catalyst according to claim 3, it is characterised in that the acid
Solution is hydrochloric acid solution, sulfuric acid solution, salpeter solution, phosphoric acid solution, the one or several kinds in trifluoromethanesulfonic acid solution.
A kind of 5. preparation method of lignin-base acidic catalyst according to claim 1, it is characterised in that the rotating speed of ball milling
For：100-650 turns/min, and Ball-milling Time is：10 minutes~96 it is small when.
6. a kind of application of lignin-base acidic catalyst, it is characterised in that the lignin-base acidic catalyst is used for hydrolytic lignin
Cellulose specifically follows the steps below：Lignin-base acidic catalyst and pretreated lignocellulosic are given birth to first
Substance is according to mass ratio 1：100~1：1 ratio is put on ball mill, and ball milling is carried out under the rotating speed of 100-650 turns/min, when
Between for 10 minutes~96 it is small when；Then the mixture after ball milling is transferred in ultralow acid solution, is 120~225 DEG C in temperature
In the range of, 1~480min is reacted, the solution based on reduced sugar is obtained, supernatant is taken after separation.
A kind of 7. application of lignin-base acidic catalyst according to claim 6, it is characterised in that the wood fibre
Cellulosic biomass is agricultural residue, timber and forest residue, algae, kudzu, coal, draft energy crop, lignocellulosic
Biomass, plant biomass or its mixture.
A kind of 8. application of lignin-base acidic catalyst according to claim 7, it is characterised in that the agricultural residues
The preferred maize straw of object, straw, bagasse, rice husk or rice straw；The timber and forest residue, preferably pine tree, willow, star-spangled banner
Pine, Oak Tree, sawdust, paper/paper pulp discarded object or wood-fibred；The draft energy crop, preferably switchgrass, reed canary grass or Chinese silvergrass；
The lignocellulose biomass, preferably lignin, cellulose and hemicellulose.
9. a kind of application of lignin-base acidic catalyst according to claim 6, it is characterised in that the ultralow acid is
The organic acid soln or the mixing of inorganic acid solution or the two that mass concentration is 0.001~0.1%, lignocellulose biomass
Mass concentration in ultralow acid solution is 0.1~30%.
10. a kind of application of lignin-base acidic catalyst according to claim 6, it is characterised in that the pretreatment,
Specially：Lignocellulose biomass is dried, until then water content removes dust, be put in 40 DEG C less than 10wt%
Baking oven in be dried to sample up to constant weight, then by sample comminution and cross 40 mesh sieves, drying to constant weight for drying box at 40 DEG C, described
Constant weight standard heat 1h again for sample after, example weight changes ± 0.1.
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