CN106423214A - Method for preparing carbon-based solid acid with high specific surface area and high acid content from corncob hydrolysis residues - Google Patents
Method for preparing carbon-based solid acid with high specific surface area and high acid content from corncob hydrolysis residues Download PDFInfo
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- hydrolytic residue
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011973 solid acid Substances 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 5
- 239000002253 acid Substances 0.000 title abstract description 25
- 239000000571 coke Substances 0.000 claims abstract description 47
- 238000003763 carbonization Methods 0.000 claims abstract description 32
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 76
- 239000000463 material Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000006277 sulfonation reaction Methods 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 239000003610 charcoal Substances 0.000 claims description 30
- 239000002250 absorbent Substances 0.000 claims description 28
- 230000002745 absorbent Effects 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 150000004965 peroxy acids Chemical class 0.000 claims description 12
- 238000001994 activation Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 150000001721 carbon Chemical class 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 241000238370 Sepia Species 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 230000007717 exclusion Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229960003487 xylose Drugs 0.000 description 2
- UEUIKXVPXLWUDU-UHFFFAOYSA-N 4-diazoniobenzenesulfonate Chemical class [O-]S(=O)(=O)C1=CC=C([N+]#N)C=C1 UEUIKXVPXLWUDU-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 241000772413 Lutrogale perspicillata Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing a carbon-based solid acid with high specific surface area and high acid content from corncob hydrolysis residues. The method comprises the following steps: carrying out hydrothermal carbonization on the corncob hydrolysis residues to obtain hydrothermal coke, activating the hydrothermal coke by an activator, carrying out high-temperature charring to obtain an active carbon material, and sulfonating the active carbon material to obtain the carbon-based solid acid. The method has low cost, and the carbon-based solid acid prepared through the method has the advantages of high specific surface area, high acid content and high catalysis efficiency.
Description
Technical field
The present invention relates to a kind of carbon-based solid acid preparation method, prepare high-specific surface area particularly to corncob hydrolytic residue
Peracid amount carbon-based solid acid method.
Background technology
Catalyst plays the important function accelerating reaction to carry out and improve yield, wherein acid catalyst in industrialized production
Obtain extensive research and applied in catalytic field.Conventional acid catalyst has：Dense H2SO4、H3PO4Deng.As classical acid
Catalyst, dense H2SO4There is low price, excellent catalytic effect, feature applied widely.However, traditional liquid acid catalyst
Easily pollution is produced to environment in catalytic chemistry course of reaction, and catalyst is not easy to reclaim, severe reaction conditions, locate afterwards
Science and engineering sequence is numerous and diverse, and yield is low with selective, the multiple operation such as product needed neutralization, washing, and the waste liquid reacting generation can be sternly
Heavy corrosion equipment.With the enhancing of people's environmental consciousness, and the proposition of " Green Chemistry " concept, increasing scholar endeavours
In development environment close friend, chemical industry sustainable development can be promoted new catalyst.Comparatively speaking, solid acid catalyst energy
Preferably solve these problems, there is extensive prospects for commercial application, be a kind of novel environmental friendly catalyst.Solid acid is urged
Agent is extensively applied in organic synthesis, and this mainly has benefited from such catalyst has cheap, environmental friendliness, is stale-proof
Erosion equipment, easily reclaim, reusable, catalytic reaction condition is gentle, yield and selectively high, post processing simplicity etc. many excellent
Point.Solid catalyst has the catalytic performance of uniqueness, is that liquid catalyst institute is irreplaceable.
In recent years, carbon-based solid acid catalyst has obtained extensive pass as a kind of more environmentally-friendly cheap novel solid acid
Note.According to the summary of presently relevant document, the synthetically prepared of carbon-based sulfonated solid acid mainly has two methods：One kind is first will
Material carries out incomplete carbonization, obtains carbon-based material, then this carbon-based material is passed through the concentrated sulfuric acid or oleum, organic sulfonic acid
Ester carries out sulfonated obtaining solid acid catalyst.This method is often using low toxicity or nontoxic material as target material, conventional
There are sucrose, glucose, starch, cellulose etc., but the incomplete carbonization of raw material that this preparation method first step causes is produced
The mesoporous less attachment being unfavorable for follow-up sulfonate radical, it is less to ultimately result in such solid acid catalyst specific surface area, and acid amount is relatively
Few, catalytic efficiency decreases.Another kind is first to carry out sulfonation process using large pore material to obtain solid-acid material, then will again
It carries out high temperature cabonization and prepares carbon-based solid acid.This solid acid has that catalytic efficiency is higher and the preferable advantage of stability, but
There is the shortcomings of generated time is longer, power consumption is high, expensive.Therefore, synthesize that a kind of specific surface area is larger, sour amount is more and simple
Single convenient carbon-based solid acid catalyst has more important practical significance.
Xibei Univ. of Agricultural ＆ Forest Science ＆ Technology horse sea otter etc. (Molecules, 2010 volume 15,7188-7196 page) by living
Property charcoal (AC) on prepare sulfonic acid matrix activated carbon (AC-S0 with hypophosphorous acid reduction 4- diazobenzene sulfonic acid salt3H), its specific surface area and acid
Measure all relatively low, respectively 602m2/ g and 0.64mmo1/g；East China Normal University Wu Peng etc.
(Micropor.Mesopor.Mater., 2007 volume 105,41-48 page) pass through a kind of mesoporous carbon of oleum gas phase xanthation
(CMK-3) obtain sulfonic group acidic carbon (CMK-3-S03H), its specific surface area is higher, in 1200m2/ g about, but its acid amount is relatively
Low, it is 1.3mmol/g.Takagaki etc. is prepared for carbon-based solid acid catalyst with glucose for raw material, preparation cost higher and
Cause the waste of glucose resource.
Content of the invention
For overcoming the carbon-based solid acid prepared the raw materials used high cost of carbon-based solid acid present in prior art, prepare
Specific surface area is less, the more low technical problem of sour amount, and the present invention proposes corncob hydrolytic residue and prepares high-specific surface area peracid
Amount carbon-based solid acid method, the method low cost, the carbon-based solid acid of the method preparation has high-specific surface area, peracid amount and urges
The advantages of change efficiency high.
For achieving the above object, the technical scheme is that：
Corncob hydrolytic residue prepares high-specific surface area peracid amount carbon-based solid acid method, and corncob hydrolytic residue is carried out
Obtain hydro-thermal coke after hydrothermal carbonization, carry out high temperature cabonization after described activated dose of activation process of hydro-thermal coke and obtain active carbon materials
Material, described active carbon material is carried out obtaining carbon-based solid acid after sulfonation process.
Preferably, its step is：
(1) pretreatment of corncob hydrolytic residue：Washing removes impurity present in corncob hydrolytic residue, then will wash
Grind after clean corncob hydrolysis stump is dry；
(2) hydrothermal carbonization of corncob hydrolytic residue：Pretreated corncob hydrolytic residue is added and after water, carries out water
It is dried to obtain hydro-thermal coke through filtration washing after hot carbonization；
(3) activation of hydro-thermal coke：Hydro-thermal coke is immersed to activator solution soak and be dried after activation；
(4) carbonization of hydro-thermal coke：Hydro-thermal coke after activation is carried out after high-temperature activation, washing drying and grinding is lived
Property Carbon Materials；
(5) sulfonation of absorbent charcoal material：Absorbent charcoal material is put into and carries out mixing with water after sulfonation to sulfonation agent solution
Uniformly, suction filtration, washing, be dried after obtain carbon-based solid acid.
Preferably, described corncob hydrolytic residue is that industrial corncob produces the residue producing after wood sugar.
It is further preferred that the method for washing is, with water cyclic washing to corncob hydrolytic residue described in step (1)
There is no the presence of undesired impurities.
It is further preferred that the temperature being dried in step (1) is 100-110 DEG C.
Still more preferably, the temperature being dried in step (1) is 105 DEG C.
It is further preferred that dried corncob hydrolytic residue is milled to 40～60 mesh in step (1).Reduce corn
The granular size of core hydrolytic residue, by increasing capacitance it is possible to increase the contact area of corncob hydrolytic residue and reaction solution, in subsequent reactions mistake
Reaction is enabled to more abundant, therefore corncob hydrolytic residue is further ground and screens by this experimental selection in journey.
Still more preferably, in step (1), dried corncob hydrolytic residue is milled to 40 mesh.Using grater
During grinding corncob hydrolytic residue, when increasing the mesh number grinding, mill must be extended under grater identical power
The broken time can be only achieved, and therefore selects less mesh number can reduce unnecessary energy consumption.
It is further preferred that corncob hydrolytic residue and the solid-to-liquid ratio of water are 1 in step (2):5～10, g:mL.This process
Fixing reaction vessel is carried out, adds the water yield and be not enough to be completely soaked corncob hydrolytic residue very little, add too much again
The maximum volume of reaction vessel can be exceeded, therefore tested under select the propriation.
Still more preferably, in step (2), corncob hydrolytic residue and the solid-to-liquid ratio of water are 1:6, g:mL.
It is further preferred that the device that step (2) hydrothermal carbonization uses is parr reactor.Parr reactor can provide
Controllable temperature, controllable pressure, controllable reaction time and the reaction condition being passed through inert gas, can require to adjust according to different preparations
Section reaction condition, has the advantages that ease for operation, result accuracy.
It is further preferred that the condition of step (2) hydrothermal carbonization is：It is heated to 245-255 DEG C of insulation 4 under protective atmosphere
～8h.
Still more preferably, the condition of step (2) hydrothermal carbonization is：It is heated to 250 DEG C of insulation 6h under protective atmosphere.
Still more preferably, described protective atmosphere is nitrogen, carbon dioxide, the combination of one or more of helium.
Still more preferably, described protective atmosphere is nitrogen.
It is further preferred that step (3) hydro-thermal coke is 1 with the solid-to-liquid ratio of activator solution:2～4, g:mL.According to this
Activator is added in hydro-thermal coke ratio, enables to activator and is fully absorbed by hydro-thermal coke, adds very little, hydro-thermal is burnt
Charcoal is not enough to absorb completely, adds the too many unnecessary waste that again can produce activator, therefore selects activation under this ratio.
Still more preferably, step (3) hydro-thermal coke and the solid-to-liquid ratio of activator solution are 1:2, g:mL.
It is further preferred that step (3) soak time is 24h, baking temperature is 105 DEG C.
It is further preferred that the activator of step (3) is inorganic acid.
Still more preferably, described inorganic acid is the combination of one or more of phosphoric acid, sulfuric acid, nitric acid.
It is further preferred that the device that step (4) high temperature cabonization uses is tube furnace.Tube furnace can provide superhigh temperature
Degree, the reaction condition of ultra-long time, and different heating rates can be provided as requested, in such a situa-tion can be by not
The further high temperature cabonization of material of abundant hydrothermal carbonization, improves carbonation rate, provides condition for Subsequent sulfonation.
It is further preferred that the condition of step (4) high temperature cabonization is：Protective atmosphere is heated with the speed of 5 DEG C/min
To 400～800 DEG C, it is incubated carbonization 1～8h.
Still more preferably, it is heated to 500～800 DEG C.
Still more preferably, it is heated to 600 DEG C.
Still more preferably, insulation carbonization time is 2～8h.
Still more preferably, insulation carbonization time is 4～8h.
It is further preferred that the concretely comprising the following steps of step (5)：Add absorbent charcoal material and sulfonation agent solution in flask,
Absorbent charcoal material is 1 with the solid-to-liquid ratio of sulfonation agent solution:5～10, g:ML, under the conditions of 100～200 DEG C, molten through sulfonating agent
Liquid sulfonation 5～10h, the mixed solution after sulfonation is slowly added in cold water and is constantly uniformly mixed, suction filtration, washing, baking
The black powder solid obtaining after dry is corncob hydrolytic residue solid acid.
Still more preferably, absorbent charcoal material and the solid-to-liquid ratio of sulfonation agent solution are 1:5～8, g:mL.
Still more preferably, absorbent charcoal material and the solid-to-liquid ratio of sulfonation agent solution are 1:6, g:mL.
Still more preferably, sulfonation temperature elects 150～200 DEG C as, elects 150 DEG C further as.
Still more preferably, sulfonation time elects 6～10h as.
Still more preferably, sulfonating agent is selected from the concentrated sulfuric acid, one or two combination of oleum, elects as dense further
Sulfuric acid.
A kind of carbon-based solid acid of said method preparation.
A kind of application in catalytic reaction for above-mentioned carbon-based solid acid.
A kind of catalyst, prepares according to the method described above.
Beneficial effects of the present invention are：
(1) from industrial prepare wood sugar by the use of corncob after solid waste residue as raw material, prepare carbon-based
Solid acid, not only reduces the preparation cost of solid acid to a certain extent, and improves the value of trade waste,
This meets China's current Green Sustainable target.
(2) adopt two step carbonization carbonization corncob hydrolytic residue, first pre- in a kettle. carbonization corncob hydrolytic residue
Preparation hydro-thermal coke, then adopts phosphoric acid dip method to activate hydro-thermal coke, finally adopts tube furnace high temperature cabonization to prepare carbon substrate
Material.Carbon-based material due to one step carbonization preparation does not have carbonization, and therefore it has mesoporous less, sulfonic group load capacity relatively
Low shortcoming, and carbon-based material carbonization can be made by two-step method preparation, surface generation is more mesoporous, so that carbon-based
Solid acid has bigger specific surface area, has more preferable catalytic efficiency.
(3) using two-step method preparation carbon-based material have more mesoporous, be next step sulfonation experiment sulfonic group carry
Supply more to depend on carrier so that the solid acid that the carbon-based solid acid of final preparation is prepared compared with prior art has more acid
Amount and more preferable catalytic efficiency.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment the invention will be further described.
Embodiment 1：
1. take a certain amount of sepia corncob hydrolytic residue, existed with water cyclic washing to no undesired impurities, then will
The corncob hydrolytic residue of wash clean is put in 105 DEG C of baking ovens and is dried, and removes moisture removal, dried corncob hydrolytic residue is existed
It is milled to 40～60 mesh in grater and is respectively put into standby in hermetic bag, the corncob hydrolytic residue 10g weighing 40 mesh is as former
Material；
2. the 10g weighing up corncob hydrolytic residue is added in parr reactor, by solid-to-liquid ratio 1:5g/mL add go from
Sub- water, air be heated to 250 DEG C of insulation 6h in exclusion reactor, prepares hydro-thermal coke, question response terminates under nitrogen protection
Afterwards the black preparing hydro-thermal coke filtration is washed, and put into removal excessive moisture in baking oven；
3. press solid-to-liquid ratio 1:2g/mL, dried hydro-thermal coke is added to immersion 24h in 85wt% phosphoric acid, during arrival
Between after by soaked corncob hydrolytic residue in 105 DEG C of baking ovens be dried, remove excessive moisture；
4. the hydro-thermal obtaining in step 3 coke is added in tube furnace, in nitrogen shielding gas, excludes inner air tube simultaneously
It is heated to 400 DEG C with the speed of 5 DEG C/min, be incubated carbonization 4h, prepare activated carbon, and by the activated carbon preparing deionized water
After washing, and drying in 105 DEG C of baking ovens, grind into powder obtains absorbent charcoal material；
5. the absorbent charcoal material of grind into powder in step 4 is added in there-necked flask, by absorbent charcoal material and dense sulphur
Acid solution solid-to-liquid ratio is 1:5g/mL, under the conditions of 100 DEG C, through being only 98% concentrated acid sulfonation 5h, the mixed solution after sulfonation delays
Slowly be added in cold water and be constantly uniformly mixed, suction filtration, washing, dry after the black powder solid that obtains be corn
Core hydrolytic residue solid acid；
Result：By performance detection, the specific surface area that nitrogen adsorption BET tests this carbon-based solid acid recording is
2480m2/ g, this carbon-based solid acid acid that NaOH solution neutralization titration records is measured as 2.4mmol/L.
Embodiment 2：
1. take a certain amount of sepia corncob hydrolytic residue, existed with water cyclic washing to no undesired impurities, then will
The corncob hydrolytic residue of wash clean is put in 105 DEG C of baking ovens and is dried, and removes moisture removal, dried corncob hydrolytic residue is existed
It is milled to 40～60 mesh in grater and is respectively put into standby in hermetic bag, the corncob hydrolytic residue 10g weighing 40 mesh is as former
Material；
2. the 10g weighing up corncob hydrolytic residue is added in parr reactor, by solid-to-liquid ratio 1:6g/mL add go from
Sub- water, air be heated to 250 DEG C of insulation 6h in exclusion reactor, prepares hydro-thermal coke, question response terminates under nitrogen protection
Afterwards the black preparing hydro-thermal coke filtration is washed, and put into removal excessive moisture in baking oven；
3. press solid-to-liquid ratio 1:2g/mL, dried hydro-thermal coke is added to immersion 24h in 85wt% phosphoric acid, during arrival
Between after by soaked corncob hydrolytic residue in 105 DEG C of baking ovens be dried, remove excessive moisture；
4. the hydro-thermal obtaining in step 3 coke is added in tube furnace, in nitrogen shielding gas, excludes inner air tube simultaneously
It is heated to 600 DEG C with the speed of 5 DEG C/min, be incubated carbonization 6h, prepare activated carbon, and by the activated carbon preparing deionized water
After washing, and drying in 105 DEG C of baking ovens, grind into powder obtains absorbent charcoal material；
5. the absorbent charcoal material of grind into powder in step 4 is added in there-necked flask, by absorbent charcoal material and dense sulphur
Acid solution solid-to-liquid ratio is 1:6g/mL, under the conditions of 150 DEG C, through 98% concentrated acid sulfonation 6h, the mixed solution after sulfonation slowly adds
Enter in cold water and be constantly uniformly mixed, suction filtration, washing, dry after the black powder solid that obtains be corncob water
Solution residue solid acid；
Result：By performance detection, the specific surface area that nitrogen adsorption BET tests this carbon-based solid acid recording is
2570m2/ g, this carbon-based solid acid acid that NaOH solution neutralization titration records is measured as 3.6mmol/L.
Embodiment 3：
1. take a certain amount of sepia corncob hydrolytic residue, existed with water cyclic washing to no undesired impurities, then will
The corncob hydrolytic residue of wash clean is put in 105 DEG C of baking ovens and is dried, and removes moisture removal, dried corncob hydrolytic residue is existed
It is milled to 40～60 mesh in grater and is respectively put into standby in hermetic bag, the corncob hydrolytic residue 10g weighing 50 mesh is as former
Material；
2. the 10g weighing up corncob hydrolytic residue is added in parr reactor, by solid-to-liquid ratio 1:7g/mL add go from
Sub- water, air be heated to 250 DEG C of insulation 6h in exclusion reactor, prepares hydro-thermal coke, question response terminates under nitrogen protection
Afterwards the black preparing hydro-thermal coke filtration is washed, and put into removal excessive moisture in baking oven；
3. press solid-to-liquid ratio 1:3g/mL, dried hydro-thermal coke is added to immersion 24h in 85wt% phosphoric acid, during arrival
Between after by soaked corncob hydrolytic residue in 105 DEG C of baking ovens be dried, remove excessive moisture；
4. the hydro-thermal obtaining in step 3 coke is added in tube furnace, in nitrogen shielding gas, excludes inner air tube simultaneously
It is heated to 600 DEG C with the speed of 5 DEG C/min, be incubated carbonization 8h, prepare activated carbon, and by the activated carbon preparing deionized water
After washing, and drying in 105 DEG C of baking ovens, grind into powder obtains absorbent charcoal material；
5. the absorbent charcoal material of grind into powder in step 4 is added in there-necked flask, by absorbent charcoal material and dense sulphur
Acid solution solid-to-liquid ratio is 1:7g/mL, under the conditions of 200 DEG C, through 98% concentrated acid sulfonation 7h, the mixed solution after sulfonation slowly adds
Enter in cold water and be constantly uniformly mixed, suction filtration, washing, dry after the black powder solid that obtains be corncob water
Solution residue solid acid；
Result：By performance detection, the specific surface area that nitrogen adsorption BET tests this carbon-based solid acid recording is
2550m2/ g, this carbon-based solid acid acid that NaOH solution neutralization titration records is measured as 2.8mmol/L.
Embodiment 4：
1. take a certain amount of sepia corncob hydrolytic residue, existed with water cyclic washing to no undesired impurities, then will
The corncob hydrolytic residue of wash clean is put in 105 DEG C of baking ovens and is dried, and removes moisture removal, dried corncob hydrolytic residue is existed
It is milled to 40～60 mesh in grater and is respectively put into standby in hermetic bag, the corncob hydrolytic residue 10g weighing 50 mesh is as former
Material；
2. the 10g weighing up corncob hydrolytic residue is added in parr reactor, by solid-to-liquid ratio 1:8g/mL add go from
Sub- water, air be heated to 250 DEG C of insulation 6h in exclusion reactor, prepares hydro-thermal coke, question response terminates under nitrogen protection
Afterwards the black preparing hydro-thermal coke filtration is washed, and put into removal excessive moisture in baking oven；
3. press solid-to-liquid ratio 1:3g/mL, dried hydro-thermal coke is added to immersion 24h in 85wt% phosphoric acid, during arrival
Between after by soaked corncob hydrolytic residue in 105 DEG C of baking ovens be dried, remove excessive moisture；
4. the hydro-thermal obtaining in step 3 coke is added in tube furnace, in nitrogen shielding gas, excludes inner air tube simultaneously
It is heated to 700 DEG C with the speed of 5 DEG C/min, be incubated carbonization 8h, prepare activated carbon, and by the activated carbon preparing deionized water
After washing, and drying in 105 DEG C of baking ovens, grind into powder obtains absorbent charcoal material；
5. the absorbent charcoal material of grind into powder in step 4 is added in there-necked flask, by absorbent charcoal material and dense sulphur
Acid solution solid-to-liquid ratio is 1:8g/mL, under the conditions of 100 DEG C, through 98% concentrated acid sulfonation 8h, the mixed solution after sulfonation slowly adds
Enter in cold water and be constantly uniformly mixed, suction filtration, washing, dry after the black powder solid that obtains be corncob water
Solution residue solid acid；
Result：By performance detection, the specific surface area that nitrogen adsorption BET tests this carbon-based solid acid recording is
2510m2/ g, this carbon-based solid acid acid that NaOH solution neutralization titration records is measured as 3.0mmol/L.
Embodiment 5：
1. take a certain amount of sepia corncob hydrolytic residue, existed with water cyclic washing to no undesired impurities, then will
The corncob hydrolytic residue of wash clean is put in 105 DEG C of baking ovens and is dried, and removes moisture removal, dried corncob hydrolytic residue is existed
It is milled to 40～60 mesh in grater and is respectively put into standby in hermetic bag, the corncob hydrolytic residue 10g weighing 60 mesh is as former
Material；
2. the 10g weighing up corncob hydrolytic residue is added in parr reactor, by solid-to-liquid ratio 1:9g/mL add go from
Sub- water, air be heated to 250 DEG C of insulation 6h in exclusion reactor, prepares hydro-thermal coke, question response terminates under nitrogen protection
Afterwards the black preparing hydro-thermal coke filtration is washed, and put into removal excessive moisture in baking oven；
3. press solid-to-liquid ratio 1:4g/mL, dried hydro-thermal coke is added to immersion 24h in 85wt% phosphoric acid, during arrival
Between after by soaked corncob hydrolytic residue in 105 DEG C of baking ovens be dried, remove excessive moisture；
4. the hydro-thermal obtaining in step 3 coke is added in tube furnace, in nitrogen shielding gas, excludes inner air tube simultaneously
It is heated to 800 DEG C with the speed of 5 DEG C/min, be incubated carbonization 6h, prepare activated carbon, and by the activated carbon preparing deionized water
After washing, and drying in 105 DEG C of baking ovens, grind into powder obtains absorbent charcoal material；
5. the absorbent charcoal material of grind into powder in step 4 is added in there-necked flask, by absorbent charcoal material and dense sulphur
Acid solution solid-to-liquid ratio is 1:9g/mL, under the conditions of 150 DEG C, through 98% concentrated acid sulfonation 9h, the mixed solution after sulfonation slowly adds
Enter in cold water and be constantly uniformly mixed, suction filtration, washing, dry after the black powder solid that obtains be corncob water
Solution residue solid acid；
Result：By performance detection, the specific surface area that nitrogen adsorption BET tests this carbon-based solid acid recording is
2470m2/ g, this carbon-based solid acid acid that NaOH solution neutralization titration records is measured as 2.6mmol/L.
Embodiment 6：
1. take a certain amount of sepia corncob hydrolytic residue, existed with water cyclic washing to no undesired impurities, then will
The corncob hydrolytic residue of wash clean is put in 105 DEG C of baking ovens and is dried, and removes moisture removal, dried corncob hydrolytic residue is existed
It is milled to 40～60 mesh in grater and is respectively put into standby in hermetic bag, the corncob hydrolytic residue 10g weighing 60 mesh is as former
Material；
2. the 10g weighing up corncob hydrolytic residue is added in parr reactor, by solid-to-liquid ratio 1:10g/mL addition is gone
Ionized water, under nitrogen protection exclusion reactor in air and be heated to 250 DEG C insulation 6h, prepare hydro-thermal coke, question response tie
After bundle, the black preparing hydro-thermal coke filtration is washed, and put into removal excessive moisture in baking oven；
3. press solid-to-liquid ratio 1:4g/mL, dried hydro-thermal coke is added to immersion 24h in 85wt% phosphoric acid, during arrival
Between after by soaked corncob hydrolytic residue in 105 DEG C of baking ovens be dried, remove excessive moisture；
4. the hydro-thermal obtaining in step 3 coke is added in tube furnace, in nitrogen shielding gas, excludes inner air tube simultaneously
It is heated to 800 DEG C with the speed of 5 DEG C/min, be incubated carbonization 6h, prepare activated carbon, and by the activated carbon preparing deionized water
After washing, and drying in 105 DEG C of baking ovens, grind into powder obtains absorbent charcoal material；
5. the absorbent charcoal material of grind into powder in step 4 is added in there-necked flask, by absorbent charcoal material and dense sulphur
Acid solution solid-to-liquid ratio is 1:10g/mL, under the conditions of 200 DEG C, through 98% concentrated acid sulfonation 10h, the mixed solution after sulfonation is slow
Be added in cold water and be constantly uniformly mixed, suction filtration, washing, dry after the black powder solid that obtains be corncob
Hydrolytic residue solid acid；
Result：By performance detection, the specific surface area that nitrogen adsorption BET tests this carbon-based solid acid recording is
2490m2/ g, this carbon-based solid acid acid that NaOH solution neutralization titration records is measured as 2.7mmol/L.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to invention protection domain
Restriction, one of ordinary skill in the art should be understood that, on the basis of technical scheme, those skilled in the art are not required to
The various modifications that creative work to be paid can be made or deformation are still within the scope of the present invention.
Claims (10)
1. corncob hydrolytic residue prepares high-specific surface area peracid amount carbon-based solid acid method, it is characterized in that, corncob is hydrolyzed
Residue obtains hydro-thermal coke after carrying out hydrothermal carbonization, carry out high temperature cabonization and obtain after described activated dose of activation process of hydro-thermal coke
Active carbon material, described active carbon material is carried out obtaining carbon-based solid acid after sulfonation process.
2. corncob hydrolytic residue as claimed in claim 1 prepares high-specific surface area peracid amount carbon-based solid acid method, and it is special
Levying is, its step is：
(1) pretreatment of corncob hydrolytic residue：Washing removes impurity present in corncob hydrolytic residue, then by wash clean
Corncob hydrolysis stump dry after grind；
(2) hydrothermal carbonization of corncob hydrolytic residue：Pretreated corncob hydrolytic residue is added and after water, carries out hydro-thermal carbon
It is dried to obtain hydro-thermal coke through filtration washing after change；
(3) activation of hydro-thermal coke：Hydro-thermal coke is immersed to activator solution soak and be dried after activation；
(4) carbonization of hydro-thermal coke：Hydro-thermal coke after activation is carried out after high-temperature activation, washing drying and grinding obtains activated carbon
Material；
(5) sulfonation of absorbent charcoal material：Absorbent charcoal material is put into and carries out mixing with water after sulfonation to sulfonation agent solution,
Suction filtration, washing, be dried after obtain carbon-based solid acid.
3. corncob hydrolytic residue as claimed in claim 2 prepares high-specific surface area peracid amount carbon-based solid acid method, and it is special
Levying is, described in step (1), the method for washing is, with not having depositing of undesired impurities in water cyclic washing to corncob hydrolytic residue
?；
Or, the temperature being dried in step (1) is 100-110 DEG C；
Or, dried corncob hydrolytic residue is milled to 40～60 mesh in step (1).
4. corncob hydrolytic residue as claimed in claim 2 prepares high-specific surface area peracid amount carbon-based solid acid method, and it is special
Levying is, in step (2), corncob hydrolytic residue and the solid-to-liquid ratio of water are 1:5～10, g:mL；
Or, the device that step (2) hydrothermal carbonization uses is parr reactor；
Or, the condition of step (2) hydrothermal carbonization is：It is heated to 245-255 DEG C of insulation 4～8h under protective atmosphere.
5. corncob hydrolytic residue as claimed in claim 2 prepares high-specific surface area peracid amount carbon-based solid acid method, and it is special
Levying is, step (3) hydro-thermal coke is 1 with the solid-to-liquid ratio of activator solution:2～4, g:mL；
Or, step (3) soak time is 24h, baking temperature is 105 DEG C；
Or, the activator of step (3) is inorganic acid.
6. corncob hydrolytic residue as claimed in claim 2 prepares high-specific surface area peracid amount carbon-based solid acid method, and it is special
Levying is, the condition of step (4) high temperature cabonization is：It is heated to 400～800 DEG C with the speed of 5 DEG C/min in protective atmosphere, insulation
Carbonization 1～8h.
7. corncob hydrolytic residue as claimed in claim 2 prepares high-specific surface area peracid amount carbon-based solid acid method, and it is special
Levying is, the concretely comprising the following steps of step (5)：Absorbent charcoal material and sulfonation agent solution, absorbent charcoal material and sulfonation is added in flask
The solid-to-liquid ratio of agent solution is 1:5～10, g:ML, under the conditions of 100～200 DEG C, through sulfonation agent solution sulfonation 5～10h, sulfonation
Mixed solution afterwards is slowly added in cold water and is constantly uniformly mixed, suction filtration, washing, dry after the black powder that obtains
Shape solid is corncob hydrolytic residue solid acid.
8. a kind of carbon-based solid acid of described method preparation as arbitrary in claim 1-7.
9. application in catalytic reaction for a kind of carbon-based solid acid as claimed in claim 8.
10. a kind of catalyst, is characterized in that, according to the arbitrary described method preparation of claim 1-7.
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