CN108273526A - A kind of sulfonation carbon solid acid catalyst and its preparation method and application - Google Patents
A kind of sulfonation carbon solid acid catalyst and its preparation method and application Download PDFInfo
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- CN108273526A CN108273526A CN201810111245.XA CN201810111245A CN108273526A CN 108273526 A CN108273526 A CN 108273526A CN 201810111245 A CN201810111245 A CN 201810111245A CN 108273526 A CN108273526 A CN 108273526A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/053—Sulfates
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Abstract
Application the invention discloses carbon solid acid catalyst of a kind of sulfonation and preparation method thereof and in microcrystalline cellulose hydrolytic process.The density of the catalyst surface sulfonic acid group is 0.30 to 0.80mmol/g, and the density of oxygen-containing group is 1.00 to 2.50mmol/g, and the control of the density content of sulfonic acid group and oxygen-containing group is 1:1.25 to 1:8.33.The catalyst hydrolysis efficiency is high, and preparation process is simple, is suitble to large-scale production.
Description
Technical field
The invention belongs to solid acid catalyst technical fields, and in particular to a kind of carbon solid acid catalyst preparation of sulfonation
Method and its application in microcrystalline cellulose hydrolytic process.
Background technology
It is that its catalyzed conversion prepares bio-fuel and chemicals that lignocellulose biomass by hydrolyzation, which prepares reducing sugar,
One important step.It, can be further through biofermentation or change after lignocellulose biomass by hydrolyzation is prepared reducing sugar
Learn method for transformation prepare the bio-fuels such as ethyl alcohol, butanol, 1,4- succinic acid, formic acid, furfural, 5 hydroxymethyl furfural, levulic acid,
Petroleum base platform chemicals and chemicals, to largely reduce the dependence to fossil energy, to adjusting one-time-consumption energy
Source structure alleviates environmental crisis and brings major opportunity.
Cellulase is the ideal catalyst of hydrocellulose, and Chinese patent 201580037593.1 discloses a kind of enzymatic
The method of hydrolysis of lignocellulose material and sugar fermentation, it is then suitable with polyalcohol (especially glycerine) first with acid and/or alkali
Sequence handles ligno-cellulosic materials, and reaction then is hydrolyzed with cellulase again, can effectively realize ligno-cellulosic
The hydrolysis or liquefaction of material.Chinese patent 201710655858.5 discloses a kind of technique of the efficient enzyme hydrolysis lignocellulosic of multistage
Method.Although cellulose hydrolyzation method reaction condition is mild, the reaction time, long efficiency was low, technique and its complexity and fiber
Plain enzyme is expensive, it is difficult to carry out large-scale commercial production.Liquid acid, for example, dilute sulfuric acid, dilute hydrochloric acid, dust technology, maleic acid,
The homogeneous acids such as formic acid are the most frequently used and most effective catalysis that catalyzing hydrolysis lignocellulose-like biomass prepares reducing sugar
Agent.Chinese patent 201410845046.3,201410156496.1,201610091292.3 individually discloses homogeneous acid system and urges
Change the method that hydrocellulose prepares reducing sugar.Although liquid acid hydrolysis of lignocellulose biolobic material have it is efficient, at
This low advantage, but liquid acid can cause equipment seriously corroded, and the material of specially treated is needed to prepare reaction unit, cost is high
It is high.In addition, liquid acid is difficult to recycle, generated acid waste liquid must be concentrated and is neutralized, and increased and be processed into
Sheet and environmental pressure.And the solubility reducing sugar product such as glucose is detached with liquid acid difficulty, thus increases production cost.
Solid acid is small to equipment corrosion, is easily recycled, and is the ideal substitute of liquid acid, thus receives numerous scholars
Concern.Chinese patent 201610624249.9,201610437789.6,201710504991.0,201410275761.8 points
Do not disclose a kind of preparation method of sulfonation carbon solid acid, traditional solid acid is usually by after carbon material high temperature cabonization, then profit
With the concentrated sulfuric acid and oleum sulfonic acid group is introduced in carbon material surface under the conditions of pyroreaction.This method needs at high temperature
It carries out, thus high energy consumption, and there is large quantity of exhaust gas and acid waste liquid to generate, do not meet the theory of Modern Green Chemistry.It is thus excellent
Change catalyst preparation process, simplify catalyst preparation flow, it is extremely necessary to reduce energy consumption and reduce the generation of waste.
In addition most of sulfonation carbon solid acid all emphasizes catalyst surface acid amount, but acid amount increases and might not promote
Lignocellulose biomass by hydrolyzation carries out, and the reducing sugars such as glucose generated instead are in high sulfonic acid density catalyst agent surface pole
It easily further decomposes, the reducing sugars such as glucose is caused selectively to decline, yield reduces.
Therefore, it in order to realize the optimization of sulfonation carbon solid acid catalyst preparation process, reduces in catalyst preparation process
The generation of waste；Optimize catalyst surface structure, enhance catalyst sulfonic acid group acidity and increases auxiliary functional group and fibre
The interaction of dimension element is come while enhancing catalyst hydrolysing activity, control catalyst surface sulfonic acid density to reduce grape as far as possible
The decomposing again in catalyst surface of the reducing sugars product such as sugar improves the reducing sugars yields such as glucose.
Invention content
First purpose of the present invention is to pass through hydro-thermal one-step method with biomass-based carbon material and sulfonating agent cheap and easy to get
Sulfonation carbon solid acid catalyst is prepared, the catalyst preparation process is simple, avoids the generation of large quantity of exhaust gas and waste liquid, meets green
The social theory that colour circle is protected has good industrialization prospect.
According to a first object of the present invention, the present invention provides a kind of sulfonation carbon solid acid catalyst, the catalysis
The density of agent sulfonic acid surfactant group is 0.30 to 0.80mmol/g, and the density of oxygen-containing group is 1.00 to 2.50mmol/g, and sulphur
The control of the density content of acid groups and oxygen-containing group is 1:1.25 to 1:8.33.
Preferably, the density of catalyst surface sulfonic acid group according to the present invention is 0.40 to 0.58mmol/g, is contained
Oxygen groups density is 1.40 to 1.93mmol/g, and the control of the density content of sulfonic acid group and oxygen-containing group is 1:2.41 to 1:
4.83。
It is further preferred that catalyst surface according to the present invention has cl radical, the cl radical density is
0.50 to 2.50mmol/g.
It is further preferred that catalyst surface according to the present invention has cl radical, the cl radical density is
0.90 to 2.00mmol/g.
It is further preferred that catalyst surface according to the present invention has cl radical, the cl radical density is
1.16 to 1.84mmol/g.
According to another aspect of the present invention, it is another object of the present invention to provide a kind of sulfonation carbon solid acid to urge
The preparation method of agent, the described method comprises the following steps：
(1) using biomass class carbon-based material as raw material, after being stirred evenly with sulfonating agent in a kettle at 150~240 DEG C
Hydrothermal carbonization reacts 3~48h；
(2) it after taking out the black solid of gained in step (1), is placed in container in the baking oven that identical carburizing temperature is arranged
In continue 3~48h of standing；
(3) after reaction, it is sulphur after the black blocks of solid of gained in step (2) is ground, washing and drying
The carbon solid acid catalyst of change.
Preferably, the biomass-based carbon material described in step (1) is selected from lignocellulose-like biomass derivative, described
Its in cellulose, lignin, glucose, fructose, maltose, sucrose, starch of lignocellulose-like biomass derivative
Middle one kind.
Preferably, sulfonating agent described in step (1) is benzene sulfonic acid, p-methyl benzenesulfonic acid, sulfosalicylic acid, p-aminophenyl sulphur
The one of which of acid, metanilic acid, dodecyl benzene sulfonic acid, and biomass-based carbon material and sulfonating agent ratio are 0.25:1
To 2:1.
Preferably, it can be further added containing chlorine additive in step (1), it is described to add for aromatic rings containing chlorine containing chlorine additive
Add agent, the one of which selected from benzyl chloride, diphenyl-chloromethane, chlorobenzene, and biomass-based carbon material is with ratio containing chlorine additive
2:1 to 5:1.
The ratio proposed in the application is mass ratio, indicates biomass class carbon material with sulfonating agent and containing chlorine additive
Ratio, unit：W/W (mass/mass), for example, g/g.
Preferably, carburizing reagent described in step (1) is carried out in polytetrafluoroethyllining lining from pressure stainless steel water heating kettle,
And carbonation reaction temperature is preferably 160~200 DEG C, the carburizing reagent time is preferably 6~for 24 hours.
Preferably, at 160~200 DEG C during obtained black blocks of solid is placed in container after being carbonized described in step (2)
Continue heat treatment 6~for 24 hours, to remove the molecular weight polymers of catalyst surface attachment.
Preferably, the black blocks of solid obtained described in step (3) is polished, then with absolute ethyl alcohol and higher than 80 DEG C
Water fully washed, until after cleaning solution is in neutrality, be put in standing and drying 6h in 120 DEG C of baking ovens, you can obtain sulfonation carbon
Matter solid acid.
According to a further aspect of the present invention, it is fine in catalysis crystallite that the present invention provides the sulfonation carbon solid acid catalysts
Application in the plain hydrolytic process of dimension, the sulfonation carbon solid acid show there is good catalysis to live microcrystalline cellulose hydrolysis
Property.
The sulfonation carbon solid acid catalyst catalyzing hydrolysis microcrystalline cellulose is used invention further provides a kind of
Method, the method carries out as follows：
It is 0.2 by mass ratio:1 to 5:1 sulfonation carbon solid acid catalyst is added with microcrystalline cellulose has polytetrafluoro
In the reaction kettle of ethylene liner, be added suitable quantity of water be sealed after at 130~200 DEG C reaction 3~for 24 hours.It reacts after reaction
Kettle cooled to room temperature carries out quantitative analysis to product in liquid phase.
Preferably, microcrystalline cellulose and sulfonation carbon solid acid catalyst mass ratio are preferably 0.5 in the method:1 to
1:1。
Preferably, reaction temperature is preferably 150~170 DEG C in the method, and the reaction time is preferably 6~12h.
Advantageous effect
(1) compared to other carbonization methods, hydrothermal carbonization method remains biomass class carbon-based material largely oxygen-containing function
Group is used as adsorption functional group, and the content of the functional group can be by biomass-based carbon material and sulfonating agent ratio, carbonization instead
Temperature and carburizing reagent time adjustment are answered, to which the exposure level of catalyst and microcrystalline cellulose is optimized, hydrolysis efficiency is big
It is big to improve.
(2) exist in the prior art by using containing cl material, such as Sucralose, Chloromethyl polystyrene and polyvinyl chloride
Catalyst surface introduces cl radical to enhance catalyst activity, but above-mentioned expensive containing cl material, it is difficult to large-scale use.
And aromatic cycle compound containing chlorine cheap and easy to get and biomass-based carbon material are added in the present invention be carbonized jointly and introduce additionally
Cl radical advanced optimizes the acidity of sulfonic acid group, to further increase catalyst hydrolysing activity.This method is simple for process,
It is of low cost, it is more suitable for mass producing.
(3) due to the use of aromatic rings sulfonated derivative as sulfonating agent, therefore the carbon solid acid surfaces sulfonic group prepared
Mass contg is moderate, while assisting functional group's optimization by above-mentioned surface to ensure catalyst excellent activity, largely
Avoid due to catalyst surface sulfonic acid density is excessively high and glucose catalyst surface further be decomposed generate by-product, from
And improve glucose selective and yield.
(4) prices of raw materials needed for the catalyst are cheap, simple and easy to get.And by the carbonization of biomass-based carbon material with connect
Branch one step of sulfonating reaction is completed, and is simplified and is optimized catalyst preparation process.Catalyst preparation conditions are mild, avoid using dense sulphur
Acid and oleum avoid the generation of exhaust gas and acid waste liquid, prepared as sulfonating agent to reduce energy consumption well
Cheng Gengjia is environmentally protective, meets present social demand.
(5) catalyst surface acid amount is controllable, and concrete content can be prepared according to the requirement specifically reacted, the sulfonation of preparation
Carbon solid acid catalyst is other than being applied in cellulose hydrolysis, also in dehydration, alkylated reaction, biodiesel preparation
Etc. be with a wide range of applications.
(6) it is formed by connecting by covalent bond between the acidity of catalyst functional group and carbon skeleton, thus catalyst stability
It is higher, catalyst recycle it is easy to use after catalyst can be directly thrown into the next step after filtration washing.Work as activity
It will can restore initial activity after catalyst surface area carbon removal using chemical method when being substantially reduced.
Description of the drawings
Fig. 1 is the XRD spectra of the sulfonation carbon solid acid catalyst obtained in embodiment 2；
Fig. 2 is the thermogravimetric curve of obtained sulfonation carbon solid acid catalyst in nitrogen in embodiment 2, it is shown that certain
Stability；
Fig. 3 is the infrared spectrum of the sulfonation carbon solid acid catalyst obtained in embodiment 2, and sulfonic acid group is labelled in figure
Characteristic peak；
Fig. 4 is that obtained sulfonation carbon solid acid catalyst recycles in microcrystalline cellulose hydrolysis and makes in embodiment 2
Activity.
Specific implementation mode
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims in the term that uses should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with the technical aspect of the present invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
The density of sulfonation carbon solid acid catalyst sulfonic acid surfactant group according to the present invention is 0.30 to 0.80mmol/g,
The density of oxygen-containing group is 1.00 to 2.50mmol/g, and the control of the density content of sulfonic acid group and oxygen-containing group is 1:1.25 extremely
1:8.33；Preferably, the density of the catalyst surface sulfonic acid group is 0.40 to 0.58mmol/g, and oxygen-containing group density is
1.40 to 1.93mmol/g, and the control of the density content of sulfonic acid group and oxygen-containing group is 1:2.41 to 1:4.83.
The biomass starting material class carbon-based material of sulfonation carbon solid acid catalyst according to the present invention has a large amount of oxygen-containing
Functional group is as adsorption functional group.These oxygen-containing functional groups can effectively ensure that the exposure level of catalyst and microcrystalline cellulose
Optimized, because the oxygen-containing functional group can form hydrogen bond with oxygen-containing group on microcrystalline cellulose surface and hydrogen atom,
So that catalyst keeps being in close contact with microcrystalline cellulose, the catalytic activity of catalyst is improved.
When the density of the oxygen-containing group on sulfonation carbon solid acid catalyst surface is less than 1.00mmol/g, microcrystalline cellulose
It is relatively low with catalyst exposure level, thus hydrolysis efficiency is not high；When more than 2.50mmol/g, microcrystalline cellulose connects with catalyst
Although the degree of touching improves, sulfonic acid density is too small at this time thus hydrolysis efficiency reduces.
In addition, sulfonation carbon solid acid catalyst according to the present invention uses aromatic rings sulfonated derivative as sulfonating agent,
Therefore the carbon solid acid surfaces sulfonic acid group content prepared is moderate, if catalyst surface sulfonic acid density is excessively high, glucose
It is further decomposed in catalyst surface and generates by-product；If catalyst surface sulfonic acid density is too low, catalytic effect is inadequate
The sulfonic acid group content of ideal, suitable density helps to improve glucose selective and yield.
When the density of the sulfonic acid group on sulfonation carbon solid acid catalyst surface is less than 0.30, then catalytic effect is inadequate
Obviously；When more than 0.80mmol/g, then by-products content increases in microcrystalline cellulose cellulose hydrolysate, the choosing of target product glucose
Selecting property reduces instead with yield.
Therefore not only the respective density range of the sulfonic acid group Yu oxygen-containing group on sulfonation carbon solid acid catalyst surface needs
Other than controlling, density content between the two will also be adjusted control, could be in hydrolysis efficiency when the two ratio is moderate
And selectivity of product and yield aspects obtain best balance.Sulfonation carbon solid acid catalyst surface according to the present invention
The density content of sulfonic acid group and oxygen-containing group is 1:1.25 to 1:8.33, preferably 1:2.41 to 1:4.83.When in this range
When interior, hydrolysis efficiency, selectivity of product and yield best results；When not in this range, although can provide in a certain respect
Effect, but overall economy quality is bad.
In addition, catalyst activity can be enhanced by usually introducing cl radical in catalyst surface, often use in the prior art
Such as Sucralose, Chloromethyl polystyrene and polyvinyl chloride containing cl material as chlorine source, but above-mentioned price containing cl material
It is expensive, it is difficult to large-scale use.And aromatic cycle compound containing chlorine cheap and easy to get and biomass-based carbon materials are added in the present invention
The common carbonization of material introduces additional cl radical, advanced optimizes the acidity of sulfonic acid group, to further increase catalyst hydrolysis
Activity.This method simple process and low cost is honest and clean, is more suitable for mass producing.
It is 0.50 to 2.50mmol/ that catalyst surface according to the present invention, which has cl radical, the cl radical density,
G, when less than this range, sulfonic acid group acidity cannot significantly improve, and catalyst hydrolysing activity improves limitation.When more than this
When range, the degree of optimization of cl radical p-sulfonic acid group acidity reaches saturation, therefore catalyst water activity reaches saturation value.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence of the invention and design each falls within the present invention
Protection domain.Unless stated otherwise, the reagent and instrument used in following embodiment is commercially available product.
Prepare embodiment 1
It is 4 by mass ratio:1 glucose and p-methyl benzenesulfonic acid is stainless in the pressure certainly of the polytetrafluoroethyllining lining of 100mL
It is sufficiently mixed in steel water heating kettle uniformly, water heating kettle sealing is then placed in 180 DEG C of baking ovens hydrothermal carbonization for 24 hours.What is obtained is black
Color blocks of solid is placed in beaker and continues to continue heat treatment in 180 DEG C of baking ovens for 24 hours to remove the small of catalyst surface attachment
Molecularly Imprinted Polymer.By after obtained black bulk solid abrasive after cooling, the deionization with absolute ethyl alcohol and higher than 80 DEG C is washed
It washs until water lotion is in neutrality, the carbon solid acid of sulfonation is prepared in collection black powder dry 6h in 120 DEG C of baking ovens.
The catalyst surface sulfonic acid group and oxygen-containing group density are respectively 0.15 and 2.78mmol/g.
Prepare embodiment 2
It is 4 by mass ratio:2 glucose and p-methyl benzenesulfonic acid is stainless in the pressure certainly of the polytetrafluoroethyllining lining of 100mL
It is sufficiently mixed in steel water heating kettle uniformly, water heating kettle sealing is then placed in 180 DEG C of baking ovens hydrothermal carbonization for 24 hours.What is obtained is black
Color blocks of solid is placed in beaker and continues to continue heat treatment in 180 DEG C of baking ovens for 24 hours to remove the small of catalyst surface attachment
Molecularly Imprinted Polymer.By after obtained black bulk solid abrasive after cooling, the deionization with absolute ethyl alcohol and higher than 80 DEG C is washed
It washs until water lotion is in neutrality, the carbon solid acid of sulfonation is prepared in collection black powder dry 6h in 120 DEG C of baking ovens.
The catalyst surface sulfonic acid group and oxygen-containing group density are respectively 0.40 and 1.93mmol/g.
The XRD spectra for the sulfonation carbon solid acid catalyst that Fig. 1 is；The sulfonation carbon solid acid that Fig. 2 is is urged
Thermogravimetric curve of the agent in nitrogen shows that the solid acid catalyst has certain stability；The sulfonation carbon that Fig. 3 is
The infrared spectrum of matter solid acid catalyst is labelled with the characteristic peak of sulfonic acid group in figure；The sulfonation carbon solid acid that Fig. 4 is
The activity that catalyst recycles in microcrystalline cellulose hydrolysis, after catalyst activity reduction, in γ-penta lactones
(GVL) in after heat treatment removal catalyst surface carbon distribution, activation recovering.
Prepare embodiment 3
It is 4 by mass ratio:4 glucose, p-methyl benzenesulfonic acid and benzyl chloride 100mL polytetrafluoroethyllining lining from
It is sufficiently mixed in pressure stainless steel water heating kettle uniformly, water heating kettle sealing is then placed in 180 DEG C of baking ovens hydrothermal carbonization for 24 hours.
To black blocks of solid be placed in beaker and to continue to continue in 180 DEG C of baking ovens heat treatment attached to remove catalyst surface for 24 hours
The molecular weight polymers.By after obtained black bulk solid abrasive after cooling, with absolute ethyl alcohol and higher than 80 DEG C go from
Sub- water washing until water lotion is in neutrality, consolidate by collection black powder dry 6h in 120 DEG C of baking ovens, the carbonaceous that sulfonation is prepared
Body acid.Catalyst surface sulfonic acid group and oxygen-containing group density are respectively 0.56 and 1.42mmol/g.
Prepare embodiment 4
It is 4 by mass ratio:4:The polytetrafluoroethyllining lining of 1 glucose, p-methyl benzenesulfonic acid and benzyl chloride in 100mL
It is sufficiently mixed from pressure stainless steel water heating kettle uniformly, water heating kettle sealing is then placed in 180 DEG C of baking ovens hydrothermal carbonization for 24 hours.
Obtained black blocks of solid is placed in beaker and continues to continue in 180 DEG C of baking ovens heat treatment for 24 hours to remove catalyst surface
The molecular weight polymers of attachment.By after obtained black bulk solid abrasive after cooling, gone with absolute ethyl alcohol and higher than 80 DEG C
For ion water washing until water lotion is in neutrality, the carbonaceous of sulfonation is prepared in collection black powder dry 6h in 120 DEG C of baking ovens
Solid acid.Catalyst surface sulfonic acid group, oxygen-containing group and cl radical density are respectively 0.58,1.40 and 1.16mmol/g.
Prepare embodiment 5
It is 4 by mass ratio:4:The polytetrafluoroethyllining lining of 2 glucose, p-methyl benzenesulfonic acid and benzyl chloride in 100mL
It is sufficiently mixed from pressure stainless steel water heating kettle uniformly, water heating kettle sealing is then placed in 180 DEG C of baking ovens hydrothermal carbonization for 24 hours.
Obtained black blocks of solid is placed in beaker and continues to continue in 180 DEG C of baking ovens heat treatment for 24 hours to remove catalyst surface
The molecular weight polymers of attachment.By after obtained black bulk solid abrasive after cooling, gone with absolute ethyl alcohol and higher than 80 DEG C
For ion water washing until water lotion is in neutrality, the carbonaceous of sulfonation is prepared in collection black powder dry 6h in 120 DEG C of baking ovens
Solid acid.Catalyst surface sulfonic acid group, oxygen-containing group and cl radical density are respectively 0.58,1.40 and 1.84mmol/g.
Prepare embodiment 6
It is 4 by mass ratio:4:The polytetrafluoroethyllining lining of 4 glucose, p-methyl benzenesulfonic acid and benzyl chloride in 100mL
It is sufficiently mixed from pressure stainless steel water heating kettle uniformly, water heating kettle sealing is then placed in 180 DEG C of baking ovens hydrothermal carbonization for 24 hours.
Obtained black blocks of solid is placed in beaker and continues to continue in 180 DEG C of baking ovens heat treatment for 24 hours to remove catalyst surface
The molecular weight polymers of attachment.By after obtained black bulk solid abrasive after cooling, gone with absolute ethyl alcohol and higher than 80 DEG C
For ion water washing until water lotion is in neutrality, the carbonaceous of sulfonation is prepared in collection black powder dry 6h in 120 DEG C of baking ovens
Solid acid.Catalyst surface sulfonic acid group, oxygen-containing group and cl radical density are respectively 0.58,1.40 and 2.39mmol/g.
EXPERIMENTAL EXAMPLE 1
Sulfonation carbon solid acid that 1g is prepared in preparing embodiment 1 to 6 respectively, 0.5g microcrystalline celluloses and
20mL deionized waters are added in the reaction kettle of 40mL polytetrafluoroethyllining linings, react 12h at 150 DEG C.As a result such as the following table 1 institute
Show.
Table 1
| Microcrystalline cellulose conversion ratio | Glucose selective | |
| Prepare embodiment 1 | 56.4% | 47.6% |
| Prepare embodiment 2 | 65.1% | 63.6% |
| Prepare embodiment 3 | 48.5% | 55.2% |
| Prepare embodiment 4 | 57.2% | 51.7% |
| Prepare embodiment 5 | 62.8% | 47.4% |
| Prepare embodiment 6 | 63.1% | 46.2% |
It can be seen that from the data of table 1 and prepare embodiment 1 compared with preparing embodiment 2, although catalyst surface oxygen-containing group
Mass contg raising is conducive to catalyst and is contacted with microcrystalline cellulose, but sulfonic acid group density is too small at this time that catalyst activity is caused to drop
It is low, and glucose selective reduces.Embodiment 3 is prepared compared with preparing embodiment 2, catalyst surface oxygen-containing group content drop
It is low cause catalyst and microcrystalline cellulose exposure level further decline thus hydrolysing activity decline, and since sulfonic acid group is close
Degree increases and glucose selective reduces.Embodiment 4 is prepared compared with preparing embodiment 3, catalyst surface introduces cl radical and leads
Catalyst activity is caused to increase, and since cl radical enhancing sulfonic acid is acid, glucose selective declines.Prepare embodiment 5 and system
Standby embodiment 4 is compared, and the raising of catalyst surface cl radical density causes catalyst activity further to increase, but sulfonic acid acidity is into one
Glucose selective further decreases after step enhancing.Embodiment 6 is prepared compared with preparing embodiment 5, catalyst surface cl radical
Although density continues to increase, but the acid optimization of cl radical p-sulfonic acid group reaches saturation at this time, thus catalyst activity also reaches
To saturation value, cellulose conversion ratio is kept essentially constant with glucose selective.
Claims (10)
1. the density of a kind of sulfonation carbon solid acid catalyst, the catalyst surface sulfonic acid group is 0.30 to 0.80mmol/
The density of g, oxygen-containing group are 1.00 to 2.50mmol/g, and the control of the density content of sulfonic acid group and oxygen-containing group is 1:1.25
To 1:8.33.
2. sulfonation carbon solid acid catalyst according to claim 1, which is characterized in that the catalyst surface sulfonic acid group
Density be 0.40 to 0.58mmol/g, oxygen-containing group density is 1.40 to 1.93mmol/g, and sulfonic acid group and oxygen-containing group
Density content control be 1:2.41 to 1:4.83.
3. sulfonation carbon solid acid catalyst according to claim 1, which is characterized in that the catalyst surface has chloro
Group, the cl radical density be 0.50 to 2.50mmol/g, preferably 0.90 to 2.00mmol/g, more preferably 1.16 to
1.84mmol/g。
4. a kind of preparation method of sulfonation carbon solid acid catalyst, the described method comprises the following steps：
(1) using biomass class carbon-based material as raw material, hydro-thermal at 150~240 DEG C in a kettle after being stirred evenly with sulfonating agent
3~48h of carburizing reagent；
(2) it after taking out the black solid of gained in step (1), is placed in container in the baking oven relaying that identical carburizing temperature is arranged
It is continuous to stand 3~48h；
(3) after reaction, it is sulfonation after the black blocks of solid of gained in step (2) is ground, washing and drying
Carbon solid acid catalyst.
5. preparation method according to claim 4, which is characterized in that the biomass-based carbon material choosing described in step (1)
From lignocellulose-like biomass derivative, the lignocellulose-like biomass derivative is selected from cellulose, lignin, grape
One kind in sugar, fructose, maltose, sucrose, starch.
6. preparation method according to claim 4, which is characterized in that sulfonating agent described in step (1) is benzene sulfonic acid, to first
The one of which of benzene sulfonic acid, sulfosalicylic acid, p-aminobenzene sulfonic acid, metanilic acid, dodecyl benzene sulfonic acid, and biomass
Base carbon material and sulfonating agent ratio are 0.25:1 to 2:1.
7. preparation method according to claim 4, which is characterized in that can further be added in step (1) and be added containing chlorine
Agent, the chlorine additive that contains is the additive of aromatic rings containing chlorine, the one of which selected from benzyl chloride, diphenyl-chloromethane, chlorobenzene, and raw
Substance base carbon material is 2 with ratio containing chlorine additive:1 to 5:1.
8. preparation method according to claim 4, which is characterized in that carburizing reagent is in polytetrafluoroethyl-ne described in step (1)
Alkene liner is carried out from pressure stainless steel water heating kettle, and carbonation reaction temperature is preferably 160~200 DEG C, and the carburizing reagent time is excellent
It is selected as 6~for 24 hours；The black blocks of solid obtained after being carbonized described in step (2) continues in being placed in container at 160~200 DEG C
Heat treatment 6~for 24 hours, to remove the molecular weight polymers of catalyst surface attachment；The black obtained described in step (3) is blocky
Solid is polished, then the water with absolute ethyl alcohol and higher than 80 DEG C is fully washed, until after cleaning solution is in neutrality, is put in
Standing and drying 6h in 120 DEG C of baking ovens, you can obtain sulfonation carbon solid acid.
9. sulfonation carbon solid acid catalyst as claimed in any of claims 1 to 3 is in catalysis microcrystalline cellulose water
Application in solution preocess.
10. a kind of method using the sulfonation carbon solid acid catalyst catalyzing hydrolysis microcrystalline cellulose, the method is as follows
It carries out：
It is 0.2 by mass ratio:1 to 5:1 sulfonation carbon solid acid catalyst is added with microcrystalline cellulose has polytetrafluoroethylene (PTFE)
In the reaction kettle of liner, be added suitable quantity of water be sealed after at 130~200 DEG C reaction 3~for 24 hours, after reaction reaction kettle from
It is so cooled to room temperature, quantitative analysis is carried out to product in liquid phase；
Wherein, microcrystalline cellulose and sulfonation carbon solid acid catalyst mass ratio are preferably 0.5 in the method:1 to 1:1；
Reaction temperature is preferably 150~170 DEG C in the method, and the reaction time is preferably 6~12h.
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