CN105289655B - Solid acid catalyst HSO3-C/Fe3O4Graphene-Fe3O4/C-SO3The preparation method of H and its method for catalyzing cellulose hydrolysis - Google Patents
Solid acid catalyst HSO3-C/Fe3O4Graphene-Fe3O4/C-SO3The preparation method of H and its method for catalyzing cellulose hydrolysis Download PDFInfo
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- CN105289655B CN105289655B CN201410275781.5A CN201410275781A CN105289655B CN 105289655 B CN105289655 B CN 105289655B CN 201410275781 A CN201410275781 A CN 201410275781A CN 105289655 B CN105289655 B CN 105289655B
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Abstract
The present invention relates to solid acid catalyst HSO3‑C/Fe3O4Graphene-Fe3O4/C‑SO3The preparation method of H and its method for catalyzing cellulose hydrolysis.Catalyst of the invention has unique structure: with graphene for main charcoal skeleton, graphene upper and lower surface is grafted Fe3O4Magnetic ion, then Carbon deposition, embeds magnetic force temper Fe3O4It is avoided to contact with solution, in the layer surface further sulfonated carry active group-SO that is carbonized3H is achieved in the sandwich of huge specific surface area and its upper and lower surface, and surface acidic groups concentration is much larger than carbon nanotube based solid acid and other conventional solids acid.The yield and purity of the glucose obtained using catalyst hydrocellulose of the invention are all significantly larger than existing solid acid catalyst, and performance is stablized, can separation-recycling-is carbonized again-is acidified again etc. from solid residue and repeatedly regeneration cycle uses.
Description
Technical field
The invention belongs to green energy resource chemical fields.Particularly, the present invention relates to graphene surface carbonization embedded magnetic grains
Sub- solid acid catalyst HSO3-C/Fe3O4Graphene-Fe3O4/C-SO3The preparation method of H and its be used for catalyzing cellulose hydrolysis
Method.
Background technique
Life social development not only consumes fossil fuel excessively, causes serious energy crisis and environmental problem；Also big
The big demand for increasing people to all kinds of daily necessities.Biomass is a kind of renewable resource, acts not only as fuel, can also be with
Platform chemicals and new material are prepared by chemical conversion.Cellulose is one of chief component of biomass energy, is had
Cellulose decomposition is the hot spot of biomass research at platform chemicals by effect ground.Saccharification of cellulose can get glucose, glucose
Then platform chemicals, such as 5-HMF, levulic acid, ethylene glycol, succinic acid, glycerol, 1,3-PD and lactic acid can be converted into
Deng these compounds are the precursors of polyester, pharmacy or degradation plastic.
Traditional cellulose method for hydrolysis includes: Concentrated acid hydrolysis method, dilute acid hydrolysis method and enzyme hydrolysis method.Concentrated acid hydrolysis method skill
The present comparative maturity of art, but it is using the problems such as dangerous, difficult in the presence of corrosion and recycling to equipment, therefore it develops
There is significant limitations.The reaction temperature of dilute acid hydrolysis method is higher, and condition is violent, and the high requirements on the equipment, influence factor is more,
And the yield of sugar is lower.Although enzyme hydrolysis method sugar yield is high, 95% can be greater than, its reaction time is long, enzyme it is at high cost, therefore
Do not have the condition being widely popularized.
On the other hand, usually catalyzing hydrolysis cellulose sugar refining can be used for using solid acid catalyst, due to its nothing
Corrosivity, the features such as recyclable, catalytic efficiency and catalytic selectivity are high are considered as most potential cellulose catalytic conversion
Technology.
Currently, the solid acid for being applied to cellulose hydrolysis mainly includes H-type zeolite, transiting state metal oxide, cation
Exchanger resin, heteropoly acid and load-type solid acid etc..However the major defect of this kind of catalyst saccharification of cellulose is used to exist
In: Solid Acid Strength Measurement Based and catalytic activity reduce in water phase condition, secondly as most of solid acid surfaces do not have highly acid position
Point, or limited by structure β-Isosorbide-5-Nitrae glycosidic bond, it cannot be close to acidic site, thus these solid acids cannot be played effectively and be urged
Change effect.It can be seen that the new and effective solid acid catalyst of exploitation is cellulose hydrolysis process urgently to be resolved one important
Problem.
Graphene (Graphene) is the new material for the individual layer laminated structure being made of carbon atom, is by carbon atom with sp2
Hybridized orbit forms the flat film that hexangle type is in honeycomb lattice, is the two-dimentional material of only one carbon atom thickness so far
Material.Graphene has huge specific surface area, and stable structure, chemical inertness, thermoelectricity conductivity is high.Graphene-structured is very steady
Fixed, the connection in graphene between each carbon atom is very flexible, is the highest substance of intensity that the mankind are currently known.Graphene tool
There are good calorifics and mechanical property, and has broad application prospects.
The information for being disclosed in the background of invention technology segment is merely intended to deepen the reason to general background technique of the invention
Solution, and it is known to those skilled in the art existing to be not construed as recognizing or imply that the information is constituted in any form
Technology.
Summary of the invention
The present invention uses graphene as carrier, grafting magnetic particle, and the embedding that is carbonized, axnthation, by with interlayer
The Large ratio surface high concentration active sites magnetic solid acid catalyst of structure improves the hydrolysis efficiency of cellulose.
It is high using the graphene-based solid acid of magnetic carbon that it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of
The method for imitating catalyzing cellulose hydrolysis.
Specifically, preparing graphene surface carbonization embedded magnetic particle solids acid catalyst the present invention relates to a kind of
HSO3-C/Fe3O4Graphene-Fe3O4/C-SO3The method of H carries out magnetic grafting to graphene, by carbonizing glucose
Covering, then it is sulfonated, this method comprises:
1) with concentrated nitric acid or concentrated sulfuric acid purifying graphene；
2) dissolution graphene after purification, and by itself and NaOH and NaNO3Solution mixing, obtaining area load has Fe3O4's
Graphene solid；
3) area load there is into Fe3O4Graphene solid and glucose be uniformly mixed；
4) product obtained in step 3) is obtained into graphene surface carbonization embedded magnetic particle solids with strong sulfuric acid response
Acid catalyst HSO3-C/Fe3O4Graphene-Fe3O4/C-SO3H。
Wherein in the step 1) of this method, concentrated nitric acid or the concentrated sulfuric acid and graphite alkene reaction 6- are made under sour boiling temperature
8 hours.
NaOH and NaNO is wherein added in the step 2) of this method3Solution is until pH value of solution is 9.
Wherein used concentrated acid sulfonation 4~12 hours in the step 4) of this method.
In one embodiment of the invention, the method comprise the steps that
1) purifying graphene: graphene is placed in concentrated nitric acid (65~68%) or the concentrated sulfuric acid (95~98%), in acid
6~8h of constant temperature back flow reaction under the conditions of boiling temperature, then deionized water is washed to neutrality, is done at 40~80 DEG C in drying box
It is dry；
2) graphene after purification is put into equipped in the beaker for filling deionized water, is ultrasonically treated 10min, make it completely
It is evenly dispersed, nitrogen 10min is then passed to, FeSO is added4·7H2O (wherein graphene and FeSO4·7H2The molar ratio of O is 1:
100~1:10) in Yu Shangshu beaker, under nitrogen protection, it is made to be uniformly mixed and dissolve, be placed in 90 DEG C of water-baths；Separately by NaOH
And NaNO3(the NaOH and NaNO of addition3Molar ratio be 1:1~1:2) be dissolved in deionized water, be passed through nitrogen 10min, set
In 90 DEG C of water-baths；By mixed NaOH and NaNO3Solution is added dropwise in graphene mixed solution with slowness, while acutely
Stirring keeps logical nitrogen to drive oxygen, after completion of dropwise addition, the constant temperature 4h in 90 DEG C of water-bath, with distilled water and without water beetle during being added dropwise
Alcohol washing, drying have Fe to get to area load3O4Graphene solid；
3) area load there is into Fe for 4:1 in mass ratio3O4Graphene solid and glucose be added deionized water in, surpass
Sound 1h, it is after mixing, dry under conditions of 40~80 DEG C, it is then put into porcelain boat, is heated at 400 DEG C under argon gas protection
1~2h；
4) by the same concentrated sulfuric acid of product obtained in step 3) (> 98%) under the conditions of 120~150 DEG C constant temperature sulfonation 4~
12h, washing are dried to get graphene surface carbonization embedded magnetic particle solids acid catalyst HSO is arrived3-C/Fe3O4Graphene-
Fe3O4/C-SO3H。
Graphene surface carbonization embedded magnetic particle solids acid catalyst HSO is prepared in of the invention3-C/Fe3O4Graphite
Alkene-Fe3O4/C-SO3The method of H causes deionized water be added that catalyst and cellulose is complete wherein deionized water is added
Full submergence.
Graphene surface carbonization embedded magnetic particle solids acid catalyst HSO is prepared in of the invention3-C/Fe3O4Graphite
Alkene-Fe3O4/C-SO3In the method for H, making to be washed with distilled water is in beaker with deionized water supersound washing at least 5 times.
Graphene surface carbonization embedded magnetic particle solids acid catalyst HSO is prepared in of the invention3-C/Fe3O4Graphite
Alkene-Fe3O4/C-SO3In the method for H, the drying is drying box drying, and drying temperature is 80~110 DEG C, drying time 2
~12h.
On the other hand, the invention further relates to use graphene surface carbonization embedded magnetic particle solids acid as described above to urge
Agent HSO3-C/Fe3O4Graphene-Fe3O4/C-SO3The method of H catalyzing cellulose hydrolysis, this method comprises: with graphene table
Face carbonization embedded magnetic particle solids acid is that catalyst and cellulose are by catalyst according to mass ratio using cellulose as raw material
15:1~1:1 is mixed, and is sufficiently mixed in deionized water, and making the concentration of catalyst and cellulose is about 20g/L~100g/
Reaction is hydrolyzed in 80~120 DEG C by L, stands and collect supernatant, and the liquid for obtaining cellulose hydrolysis through centrifugal filtration produces
Object.
In the method that cellulose of the invention hydrolyzes, the hydrolysis time is 2~6h.
The present invention is using graphene surface carbonization embedded magnetic particle solids acid as catalyst, by the way that deionized water and fibre is added
It is hydrolyzed at a lower temperature after dimension element mixing, the product liquid rich in a large amount of glucose can be obtained.Graphene surface carbonization packet
Burying magnetic particle solid acid catalyst is a kind of novel catalyst, the superficial layer-carbonization of sandwich, respectively acidic-group
The magnetic particles sublayer Fe of layer-embedding3O4Graphene layer-embedding magnetic particles sublayer Fe3O4Carburization zone-acidic-group superficial layer.
It is to be grafted Fe in graphene outer surface3O4Nano particle makes catalyst have magnetism, then in Fe3O4It is cladded with one layer of glucose,
High temperature carbonization, it is last sulfonated.The glucose of catalyst charing of the invention wraps Fe3O4, prevent Fe3O4By sulfuric acid oxygen
Change；Not only it can increase specific surface area, but also be more advantageous to the load of acidic-group than graphene；It is different from carbon nanotube, graphite simultaneously
Alkene can upper and lower surface Carbon deposition acidification, hydrolysis efficiency can be improved.Of the invention uses the cellulolytic method of modified graphene
Reaction condition is mild, cellulose is hydrolyzed generate glucose have it is highly selective and small to the corrosivity of equipment, can be effective
Reduce the manufacturing cost of hydrolysis reaction device.In addition, the recyclable recycling of catalyst produced by the present invention, it can be directly using outer
Portion magnetic field separates and recovers it from hydrolytic residue, and simple process is feasible, is easy to large-scale production.
Specific embodiment
The present invention provides prepare graphene surface carbonization embedded magnetic particle solids acid catalyst HSO3-C/Fe3O4Stone
Black alkene-Fe3O4/C-SO3The method of H and the method hydrolyzed using the catalyst cellulose, below with reference to specific embodiment party
The present invention will be further described for formula.
Percentage composition in following embodiments is mass percentage unless otherwise specified.
Embodiment 1
3g graphene is weighed, the 100ml concentrated sulfuric acid (98%) is placed it in, constant temperature back flow reaction 6h under conditions of 140 DEG C,
Deionized water is washed to neutrality, the dry 12h at 80 DEG C in drying box.
It takes the modified graphene of 0.5g to be added in the aqueous solution of 100mL, is ultrasonically treated 10min, make its substantially uniformity point
It dissipates.Then pass to nitrogen 10min.
Weigh the FeSO of 0.5g4·7H2O is placed in above-mentioned beaker, under nitrogen protection, so that it is uniformly mixed and is dissolved, is put in
In 90 DEG C of water-bath.
Separately weigh 2.5g NaOH and 4.5g NaNO3It is dissolved in deionized water, is passed through nitrogen 10min, be placed in 90 DEG C of water
In bath.Then obtained solution is added dropwise in the mixed solution of above-mentioned modified graphene with slower speed, is vigorously stirred simultaneously,
Logical nitrogen is kept during being added dropwise, and after completion of dropwise addition, keeps the temperature 4h in 90 DEG C of water-bath.Deionized water supersound washing 5 times.80℃
Lower dry 12h has Fe to get to area load3O4Graphene solid.
Weighing 0.4g area load has Fe3O4Graphene powder and 0.1g glucose, add deionized water, ultrasonic 1h,
After mixing, dry 16h under conditions of 70 DEG C, is then put into porcelain boat, heats under the conditions of 400 DEG C under argon gas protection
1h；The concentrated sulfuric acid (> 98%) constant temperature sulfonation 6h under the conditions of 120 DEG C is added, benefit is washed with deionized to sulfate radical-free after cooling
Ion obtains graphene surface carbonization embedded magnetic particle solids acid catalyst after dry.
Above-mentioned 0.3g magnetic graphene based solid acid and 0.025g microcrystalline cellulose powder are mixed in 3ml deionized water
It closes, reacts 4h under conditions of 120 DEG C of temperature constant magnetic stirrings, the glucose yield for measuring cellulose is 30%.
Embodiment 2
By 0.25g magnetic graphene based solid acid obtained in embodiment 1,0.025g microcrystalline cellulose powder is gone in 3ml
It is mixed in ionized water, carries out temperature constant magnetic stirring.Isothermal reaction 5h under conditions of 100 DEG C, the glucose for measuring cellulose obtain
Rate is 28%.
Embodiment 3
By 0.2g magnetic graphene based solid acid obtained in embodiment 1,0.025g microcrystalline cellulose powder 3ml go from
It is mixed in sub- water, carries out temperature constant magnetic stirring.Isothermal reaction 8h under conditions of 120 DEG C measures the glucose yield of cellulose
It is 22%.
Claims (8)
1. a kind of prepare graphene surface carbonization embedded magnetic particle solids acid catalyst HSO3-C/Fe3O4Graphene-Fe3O4/
C-SO3The method of H, this method comprises:
1) with concentrated nitric acid or concentrated sulfuric acid purifying graphene；
2) graphene of dissolution after purification, is first added FeSO4·7H2O be uniformly mixed, then again with NaOH and NaNO3Solution is mixed
It closes, obtaining area load has Fe3O4Graphene solid；
3) area load there is into Fe3O4Graphene solid and glucose be uniformly mixed, it is dry after under argon atmosphere protection, in
It is heated 1-2 hours at 400 DEG C；
4) product obtained in step 3) graphene surface carbonization embedded magnetic particle solids acid is obtained with strong sulfuric acid response to urge
Agent HSO3-C/Fe3O4Graphene-Fe3O4/C-SO3H。
2. according to claim 1 prepare graphene surface carbonization embedded magnetic particle solids acid catalyst HSO3-C/
Fe3O4Graphene-Fe3O4/C-SO3The method of H, wherein in the step 1) of this method, make under sour boiling temperature concentrated nitric acid or
Person's concentrated sulfuric acid with graphite alkene reaction 6-8 hours.
3. according to claim 1 prepare graphene surface carbonization embedded magnetic particle solids acid catalyst HSO3-C/
Fe3O4Graphene-Fe3O4/C-SO3The method of H, wherein NaOH and NaNO is added in the step 2) of this method3Solution is until molten
Liquid pH is 9.
4. according to claim 1 prepare graphene surface carbonization embedded magnetic particle solids acid catalyst HSO3-C/
Fe3O4Graphene-Fe3O4/C-SO3The method of H, wherein being used concentrated acid sulfonation 4~12 hours in the step 4) of this method.
5. a kind of prepare graphene surface carbonization embedded magnetic particle solids acid catalyst HSO3-C/Fe3O4Graphene-Fe3O4/
C-SO3The method of H, this method comprises:
1) purifying graphene: graphene is placed in concentrated nitric acid or the concentrated sulfuric acid, and constant temperature reflux is anti-under the conditions of sour boiling temperature
6~8h is answered, then deionized water is washed to neutrality, dry at 40~80 DEG C in drying box；
2) graphene after purification is put into equipped in the beaker for filling deionized water, is ultrasonically treated 10min, makes its substantially uniformity
Dispersion then passes to nitrogen 10min, and FeSO is added4·7H2O is in above-mentioned beaker, under nitrogen protection, keeps it uniformly mixed and molten
Solution, is placed in 90 DEG C of water-baths；Separately by NaOH and NaNO3It is dissolved in deionized water, is passed through nitrogen 10min, be placed in 90 DEG C of water-baths
In；By mixed NaOH and NaNO3Solution is vigorously stirred simultaneously with being added dropwise at a slow speed in graphene mixed solution, until molten
Liquid pH is 9, keeps logical nitrogen to drive oxygen during being added dropwise, after completion of dropwise addition, the constant temperature 4h in 90 DEG C of water-bath, with distilled water and anhydrous
Methanol washing, drying have Fe to get to area load3O4Graphene solid；
3) area load there is into Fe for 4:1 in mass ratio3O4Graphene solid and glucose be added deionized water in, ultrasonic 1h,
After mixing, dry under conditions of 40~80 DEG C, be then put into porcelain boat, under argon gas protection at 400 DEG C heating 1~
2h；
4) by product obtained in step 3), with the concentrated sulfuric acid, constant temperature 4~12h of sulfonation under the conditions of 120~150 DEG C, washing are dried,
Obtain graphene surface carbonization embedded magnetic particle solids acid catalyst HSO3-C/Fe3O4Graphene-Fe3O4/C-SO3H。
6. a kind of prepare graphene surface carbonization embedded magnetic particle solids acid catalyst HSO using by as claimed in claim 43-
C/Fe3O4Graphene-Fe3O4/C-SO3The method of the hydrolysis of catalyst cellulose made from H method, this method comprises: with stone
Black alkene surface carbonation embedded magnetic particle solids acid is catalyst, using cellulose as raw material, by catalyst and cellulose according to matter
Amount is sufficiently mixed in deionized water than being that 15:1~1:1 is mixed, reaction is hydrolyzed in 80~120 DEG C, stand and receive
Collect supernatant, obtains the product liquid of cellulose hydrolysis through centrifugal filtration.
7. according to the method described in claim 6, the amount that deionized water is wherein added is to cause deionized water be added that can incite somebody to action
Catalyst and cellulose are totally submerged.
8. the method for cellulose hydrolysis according to claim 6, wherein the hydrolysis time is 2~6h.
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| CN107858457A (en) * | 2017-11-14 | 2018-03-30 | 天津工业大学 | A kind of method of high dispersive sulfoxidation graphene catalyzing hydrolysis cellulose |
| CN109777896A (en) * | 2019-02-27 | 2019-05-21 | 天津大学 | The method that magnetic solid acid catalyzing cellulose hydrolysis prepares glucose |
| CN110420663B (en) * | 2019-08-15 | 2021-01-12 | 山东大学 | Composite catalyst for producing small molecular acid by efficiently catalyzing and degrading straw and preparation method thereof |
| CN114345341B (en) * | 2020-10-13 | 2024-01-19 | 中石化南京化工研究院有限公司 | Graphene coated solid acid catalyst and preparation method thereof |
| CN114522701B (en) * | 2022-04-22 | 2022-08-09 | 浙江晟格生物科技有限公司 | Compound sulfate radical catalyst for biological sugar preparation, preparation method and application |
| CN114984957B (en) * | 2022-07-06 | 2023-09-01 | 东北电力大学 | Preparation method of heteropolyacid photocatalyst capable of being magnetically regulated and controlled |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881898A (en) * | 2012-09-17 | 2013-01-16 | 上海交通大学 | Preparation method and application of carbon-coated grapheme-based metal oxide composite |
| JP2013035743A (en) * | 2011-07-12 | 2013-02-21 | Institute Of National Colleges Of Technology Japan | Carbonaceous composite, and method for manufacturing the same |
| CN103021503A (en) * | 2011-09-26 | 2013-04-03 | 国家纳米科学中心 | Graphene-carbon nano composite transparent conducting thin film and preparation method thereof |
| JP5357323B1 (en) * | 2012-12-27 | 2013-12-04 | 株式会社Ｍｉｃｃ Ｔｅｃ | Method for producing graphene oxide |
-
2014
- 2014-06-19 CN CN201410275781.5A patent/CN105289655B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013035743A (en) * | 2011-07-12 | 2013-02-21 | Institute Of National Colleges Of Technology Japan | Carbonaceous composite, and method for manufacturing the same |
| CN103021503A (en) * | 2011-09-26 | 2013-04-03 | 国家纳米科学中心 | Graphene-carbon nano composite transparent conducting thin film and preparation method thereof |
| CN102881898A (en) * | 2012-09-17 | 2013-01-16 | 上海交通大学 | Preparation method and application of carbon-coated grapheme-based metal oxide composite |
| JP5357323B1 (en) * | 2012-12-27 | 2013-12-04 | 株式会社Ｍｉｃｃ Ｔｅｃ | Method for producing graphene oxide |
Non-Patent Citations (1)
| Title |
|---|
| Graphene oxide for cellulose hydrolysis: how it works as a highly active catalyst;Xiaochen Zhao等;《Chem. Commun.》;20140210;第50卷;第3439--3442页 |
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