CN107442068A - Micro- mesoporous activated carbon/the SiO of nanometer is prepared using black liquid2Composite and its application - Google Patents
Micro- mesoporous activated carbon/the SiO of nanometer is prepared using black liquid2Composite and its application Download PDFInfo
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
Abstract
The invention belongs to field of nanometer material technology, specifically discloses and prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2Composite and its application.Described prepares the micro- mesoporous activated carbon/SiO of nanometer using papermaking digesting black liquor2The method of composite is divided into two steps：The first step is to prepare lignin/SiO using black liquid2Composite powder；Second step is with gained lignin/SiO2Composite powder is raw material, adds composite activating agent, and pyroreaction obtains the micro- mesoporous activated carbon/SiO of nanometer2Composite.Micro- mesoporous activated carbon/the SiO of nanometer2Composite material and preparation method thereof is simple, does not only reach nano-scale, and chemical stability, absorption property are excellent, can be incorporated in sewage disposal, deodorization taste removal extensively or as raw material of industry etc..
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to one kind using black liquid prepare nanometer micro- mesoporous activated carbon/
SiO2The method of composite and application.
Background technology
New and high technology material of the nano material as century, because of its distinctive skin effect, small-size effect, quantum effect
With optical characteristics etc., turn into the focus of materials science field research.The micro- mesoporous material of nanometer has highly developed pore structure
With special surface property, its internal pore structure with uniqueness and huge specific surface area, therefore be widely used in inhaling
Attached dose, the carrier of catalyst and catalyst, have become the essential product in the fields such as environmental protection, food, chemical industry.
Nano silicon is one of ultra tiny New Inorganic Materials of extremely important high-tech, because of its particle diameter very little, compares table
Area is big, and superficial attractive forces are strong, and surface energy is big, chemical purity is high, dispersive property is good, thermal resistance, resistance etc. have it is special
Performance, with its superior stability, reinforcing, thickening property and thixotropy, show unique characteristics, have not in numerous subjects and field
Commutable effect, every profession and trade is widely used in as additive, catalyst carrier, petrochemical industry, ink thickeners, insulation and thermal insulation
Filler, the various fields such as high-grade daily-use cosmetics filler and sprayed on material, medicine, environmental protection.
Porous charcoal is applied to various fields due to the pore structure with prosperity and superhigh specific surface area, big according to aperture
It is small to be divided into micropore (d ＜ 2nm), mesoporous (2nm ＜ d ＜ 50nm) and macropore (d ＞ 50nm), different pore structure in porous charcoal
Presence determine its purposes in different field.Different material and activation method directly affect the structural behaviour of activated carbon,
So as to affect its application performance.
Micro- mesoporous activated carbon/the SiO of nanometer2A large amount of nano-pores in composite be present, have specific surface area is big, pore volume is high,
The features such as good fluidity and the easy functionalization in surface, have in adsorbing separation, catalyst carrier, thermal resistance and medicine controlled release etc.
Have broad application prospects.
The developed country such as the U.S. and Japan can successfully prepare high specific surface area porous charcoal, and its raw material is mostly pitch, coal
The of a relatively high fossil resource raw material of the carbon content such as charcoal and petroleum coke, but in industrial production and application process porous charcoal into
This is too high, and regeneration is difficult, therefore finds cheap raw material and the method for rationally preparing high specific surface area porous charcoal,
Porous charcoal is set widely to be applied to more areas, such as battery and electrode material for super capacitor, catalyst carrier, energy storage material
Material, this has turned into the problem of domestic and international primary study.Statistics shows that world community man is to the demand speed of porous charcoal not
Disconnected to increase, China is used as porous charcoal demand big country, and it is highly important to research and produce a great amount of high specific surface area porous charcoal.
The content of the invention
The shortcomings that in order to overcome existing raw material and technology and deficiency, primary and foremost purpose of the invention are that providing a kind of utilize makes
Prepared by paper black liquor has the micro- mesoporous composite of nanometer：Micro- mesoporous activated carbon/the SiO of nanometer2Composite.
Another object of the present invention is to provide above-mentioned utilization black liquid to prepare the micro- mesoporous activated carbon/SiO of nanometer2It is compound
The preparation method of material.This method uses KOH and CO2Lignin/SiO in concerted catalysis black liquid2Compound, it is to alkali
The efficient green recycling application of method black liquid.
Another object of the present invention is the micro- mesoporous activated carbon/SiO of above-mentioned nanometer2The application of composite.
For achieving the above object, the present invention adopts the following technical scheme that：
One kind prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2The preparation method of composite, including it is as follows
Step：
(1) lignin/SiO is collected from black liquid2Compound, then by lignin/SiO2It is dry that compound carries out freezing
It is dry, then crushed to obtain powder；
(2) appropriate lignin/SiO is taken2Composite powder is put into Muffle furnace, introduces composite activating agent KOH and CO2, calcination
Certain time obtains the micro- mesoporous activated carbon/SiO of nanometer after taking out cooling2Composite.
Preferably, the temperature of step (1) described freeze-drying is -10~-60 DEG C, and vacuum is 1.3~10Pa, and the time is
12~48h；More preferably -40 DEG C of temperature, vacuum 2Pa, time 24h.
Preferably, CO in the composite activating agent described in step (2)2Intake is 0.1-10.0L/min.
Preferably, KOH and lignin/SiO in the composite activating agent described in step (2)2Compound mass ratio for (0.5~
5)：1, more preferably 1:1.
Preferably, the temperature of the calcination described in step (2) is 500~800 DEG C, more preferably 600 DEG C.
Preferably, the time of the calcination described in step (2) is 1~5h, more preferably 2h.
Present invention also offers a kind of micro- mesoporous activated carbon/SiO of nanometer2Composite.
Micro- mesoporous activated carbon/the SiO of above-mentioned nanometer2Composite does not only reach nano-scale, and chemical stability, absorption
Excellent performance, it can be applied in fields such as environmental protection, medicine, military affairs, chemical industry, such as sewage disposal, deodorization taste removal or conduct industry
Raw material.
Present invention utilizes the lignin and silicon contained in alkaline pulping black liquor, by isolated lignin/SiO2
Compound, then using the compound as raw material, the micro- mesoporous activated carbon/SiO of nanometer is prepared under activator effect2Composite.
The characteristic of the materials combine activated carbon and silica, there is high reference area and absorption property.
One kind of the present invention prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2The method of composite,
In practical operation, raw material can be the raw pulp black liquor such as straw pulp of rice and wheat black liquor or timber, bamboo, reed, different
Raw material prepares products obtained therefrom and slightly has difference.
Compared with prior art, the present invention has advantages below and beneficial effect：
C/SiO2Composite is similar before this to report (the pure as jade carbon point/mesoporous SiO 2 composite of horse
Prepare and performance study Shandong University .2013.), but its method is sol-gel process, i.e. synthetic vectors and carbon source first,
Then the two reaction is mixed again, operating procedure is complicated.The present invention is former better than rice straw paper making from black liquor of pulp making
Element silicon is rich in material, causes to be rich in silicon and lignin in alkaline cooking black liquor, lignin and dioxy is obtained by proper treatment
The compound of SiClx, activated carbon is prepared as raw material.Silica is introduced during activated carbon is prepared, makes full use of wood
The stickiness and macromolecular network characteristic that element has in itself, by SiO2Effectively it is coated on inside the grid of macromolecular formation,
Promote two kinds of materials to be effectively combined together, mutually produce synergetic, add the chemical stability of activated carbon, form
Nanometer is micro- mesoporous.In addition, synergistic catalyst, i.e. KOH and CO are innovatively used in the present invention2Co-catalysis, on the one hand realize section
The purpose of chemicals is saved, reaction activity is on the other hand reduced, is easier to make for reaction, so as to save the energy.By aperture
Knowable to distribution map 2, activated carbon/SiO prepared by the present invention2Composite wood blanking aperture≤50nm, reference area is up to 600m2/g.Hole
Footpath distribution absolutely proves activated carbon/SiO2The pore-size distribution of composite is very wide, belongs to a kind of micro- mesoporous material coexisted.
The present invention can prepare active adsorbing material as a kind of green resource application of black liquor of pulp making, not only reduce
Pollution of the black liquid to environment, intractability is reduced, turns waste into wealth, makes utilization of resources, also expand and prepare activated carbon
The range of choice of raw material.
Method of the present invention, in practical operation, raw material can be the non-wood-fibers such as rice wheat straw, bamboo, reed
The black liquor of pulp making or wood raw material black liquor of pulp making of raw material, different material prepares products obtained therefrom and slightly has difference, but prepares
Technique is essentially identical.
Brief description of the drawings
Fig. 1 is the micro- mesoporous activated carbon/SiO of nanometer of embodiment 12The preparation process schematic diagram of composite.
Fig. 2 is the micro- mesoporous activated carbon/SiO of nanometer2The graph of pore diameter distribution of composite.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.Unless otherwise instructed, the percentage described in embodiment is all mass percent.
Each initiation material is commercially available or prepared according to art methods in preparation method of the present invention.At this
In embodiment, lignin/SiO2The preparation of compound may be referred to it has been reported that method obtain that (Qu Yuning lignin carries
Take and application [J] the Jilin University .2012.6 in polyurethane, 10-14.), but lignin/SiO2The preparation method of compound
It is not limited to this kind of mode.The present invention prepares lignin/SiO using following steps2Compound：
(1) black liquor collected in paper-making process during alkaline cooking is kept into constant temperature in reaction vessel, is during which passed through inertia
Gas shield, the pH of acid adding regulation black liquor is in acidity；
(2) black liquor is cooled down, it is settled a period of time after reacting, makes lignin/SiO in black liquor2Sedimentation is complete；
(3) supernatant liquor is poured out after black liquor is centrifuged, is washed with water, is centrifuged again according to aforesaid operations for several times, until
PH is neutrality, and it is lignin/SiO to collect lower floor's material2Compound.
Black liquor keeping temperature described in step (1) is 60 DEG C；The black liquor pH value acid adding is adjusted to 3.
Described in step (1) during alkaline cooking, alkali charge is 8~12% relative to over dry straw quality, anthraquinone phase
It is 0.01~0.2% for over dry straw quality, liquor ratio 1：(5~8), 1~3h of heating-up time, boiling maximum temperature 140~165
DEG C, 0~1h of soaking time；Preferably alkali charge is 10% relative to over dry straw quality, and anthraquinone is relative to over dry straw quality
For 0.1%, liquor ratio 1：6, heating-up time 2h, 155 DEG C of boiling maximum temperature, soaking time 0.5h.
Acid described in step (1) is preferably sulfuric acid, and mass fraction is 1~5%, can also use hydrochloric acid, phosphoric acid and nitric acid etc.
Instead of；Sulfuric acid mass fraction is preferably 5%.
Sedimentation time described in step (2) is 1~5h；Preferably 3h.
In step (3) described centrifugally operated, 5000~10000r/min of rotating speed, centrifugation time is 5~30min；Preferably
Centrifugal rotational speed 8000r/min, time 10min.
Embodiment 1
(1) it is raw material to weigh 500g straw, alkaline cooking, and alkali charge is relative to the 14% of over dry straw quality, anthraquinone phase
For the 0.1% of over dry straw quality, liquor ratio 1：5, heating-up time 2h, 155 DEG C, soaking time 0.5h of boiling maximum temperature, receive
Collect black liquor；Black liquor is heated to 60 DEG C of holding constant temperature in there-necked flask, is during which passed through nitrogen protection, acid adding adjusts the pH=of black liquor
3.Black liquor is cooled down, it is settled 3h after reacting, makes lignin/SiO in black liquor2Sedimentation is complete.Black liquor is centrifuged,
Rotating speed 8000r/min, centrifugation time 10min, supernatant liquor is poured out after centrifugation, is washed with deionized, according to aforesaid operations
Centrifuge again for several times, until pH is neutrality, it is lignin/SiO to collect lower floor's material2Compound.By lignin/SiO2Compound-
10 DEG C, be freeze-dried 48h under vacuum 1.3Pa, obtain lignin/SiO2Compound, it is ground with mortar to obtain powder.
(2) 2.0000g lignin/SiO is taken2Composite powder is put into Muffle furnace, when introducing one section of activator KOH calcinations
Between, KOH and lignin/SiO2The mass ratio of composite powder is 2：1, the temperature of calcination is 650 DEG C, and soak time is
1.5h, the micro- mesoporous activated carbon/SiO of nanometer is obtained after taking out cooling after arrival time2Composite.
Embodiment 2
(1) it is raw material to weigh 500g straw, alkaline cooking, and alkali charge is relative to the 14% of over dry straw quality, anthraquinone phase
For the 0.1% of over dry straw quality, liquor ratio 1：5, heating-up time 2h, 155 DEG C, soaking time 0.5h of boiling maximum temperature, receive
Collect black liquor；Black liquor is heated to 60 DEG C of holding constant temperature in there-necked flask, is during which passed through nitrogen protection, acid adding adjusts the pH=of black liquor
3.Black liquor is cooled down, it is settled 3h after reacting, makes lignin/SiO in black liquor2Sedimentation is complete.Black liquor is centrifuged,
Rotating speed 8000r/min, centrifugation time 10min, supernatant liquor is poured out after centrifugation, is washed with deionized, according to aforesaid operations
Centrifuge again for several times, until pH is neutrality, it is lignin/SiO to collect lower floor's material2Compound.By lignin/SiO2Compound-
10 DEG C, be freeze-dried 48h under vacuum 1.3Pa, obtain lignin/SiO2Compound, it is ground with mortar to obtain powder.
(2) 2.0000g lignin/SiO is taken2Composite powder is put into Muffle furnace, introduces activator CO2During one section of calcination
Between, CO2Intake is 1.0L/min, and the temperature of calcination is 600 DEG C, soak time 2h, is obtained after cooling is taken out after arrival time
To the micro- mesoporous activated carbon/SiO of nanometer2Composite.
Embodiment 3
Preparation process is as shown in Figure 1：
(1) it is raw material to weigh 500g straw, alkaline cooking, and alkali charge is relative to the 14% of over dry straw quality, anthraquinone phase
For the 0.1% of over dry straw quality, liquor ratio 1：5, heating-up time 2h, 155 DEG C, soaking time 0.5h of boiling maximum temperature, receive
Collect black liquor；Black liquor is heated to 60 DEG C of holding constant temperature in there-necked flask, is during which passed through nitrogen protection, acid adding adjusts the pH=of black liquor
3.Black liquor is cooled down, it is settled 3h after reacting, makes lignin/SiO in black liquor2Sedimentation is complete.Black liquor is centrifuged,
Rotating speed 8000r/min, centrifugation time 10min, supernatant liquor is poured out after centrifugation, is washed with deionized, according to aforesaid operations
Centrifuge again for several times, until pH is neutrality, it is lignin/SiO to collect lower floor's material2Compound.By lignin/SiO2Compound-
10 DEG C, be freeze-dried 48h under vacuum 1.3Pa, obtain lignin/SiO2Compound, it is ground with mortar to obtain powder.
(2) 2.0000g lignin/SiO is taken2Composite powder is put into Muffle furnace, introduces composite activating agent KOH and CO2Burn
Burn a period of time；CO2Intake is 0.1L/min, KOH and lignin/SiO2The mass ratio of composite powder is 0.5：1, burn
The temperature of burning is 700 DEG C, soak time 1h, and the micro- mesoporous activated carbon/SiO of nanometer is obtained after taking out cooling after arrival time2It is multiple
Condensation material.
Embodiment 4
(1) it is raw material to weigh 500g straw, alkaline cooking, and alkali charge is relative to the 14% of over dry straw quality, anthraquinone phase
For the 0.1% of over dry straw quality, liquor ratio 1：5, heating-up time 2h, 155 DEG C, soaking time 0.5h of boiling maximum temperature, receive
Collect black liquor；Black liquor is heated to 60 DEG C of holding constant temperature in there-necked flask, is during which passed through nitrogen protection, acid adding adjusts the pH=of black liquor
3.Black liquor is cooled down, it is settled 3h after reacting, makes lignin/SiO in black liquor2Sedimentation is complete.Black liquor is centrifuged,
Rotating speed 8000r/min, centrifugation time 10min, supernatant liquor is poured out after centrifugation, is washed with deionized, according to aforesaid operations
Centrifuge again for several times, until pH is neutrality, it is lignin/SiO to collect lower floor's material2Compound.By lignin/SiO2Compound-
30 DEG C, be freeze-dried 24h under vacuum 5Pa, obtain lignin/SiO2Compound, it is ground with mortar to obtain powder.
(2) 2.0000g lignin/SiO is taken2Composite powder is put into Muffle furnace, introduces composite activating agent KOH and CO2Burn
Burn a period of time；CO2Intake is 0.3L/min, KOH and lignin/SiO2The mass ratio of composite powder is 1：1, calcination
Temperature be 800 DEG C, soak time 2h, after arrival time take out cooling after obtain the micro- mesoporous activated carbon/SiO of nanometer2It is compound
Material.
Embodiment 5
(1) it is raw material to weigh 500g straw, alkaline cooking, and alkali charge is relative to the 14% of over dry straw quality, anthraquinone phase
For the 0.1% of over dry straw quality, liquor ratio 1：5, heating-up time 2h, 155 DEG C, soaking time 0.5h of boiling maximum temperature, receive
Collect black liquor；Black liquor is heated to 60 DEG C of holding constant temperature in there-necked flask, is during which passed through nitrogen protection, acid adding adjusts the pH=of black liquor
3.Black liquor is cooled down, it is settled 3h after reacting, makes lignin/SiO in black liquor2Sedimentation is complete.Black liquor is centrifuged,
Rotating speed 8000r/min, centrifugation time 10min, supernatant liquor is poured out after centrifugation, is washed with deionized, according to aforesaid operations
Centrifuge again for several times, until pH is neutrality, it is lignin/SiO to collect lower floor's material2Compound.By lignin/SiO2Compound-
60 DEG C, be freeze-dried 12h under vacuum 2Pa, obtain lignin/SiO2Compound, it is ground with mortar to obtain powder.
(2) 2.0000g lignin/SiO is taken2Composite powder is put into Muffle furnace, introduces composite activating agent KOH and CO2Burn
Burn a period of time；KOH and lignin/SiO2The mass ratio of composite powder is 3：1, CO2Intake is 0.8L/min, calcination
Temperature be 600 DEG C, soak time 3h, after arrival time take out cooling after obtain the micro- mesoporous activated carbon/SiO of nanometer2It is compound
Material.
Embodiment 6
(1) it is raw material to weigh 500g straw, alkaline cooking, and alkali charge is relative to the 14% of over dry straw quality, anthraquinone phase
For the 0.1% of over dry straw quality, liquor ratio 1：5, heating-up time 2h, 155 DEG C, soaking time 0.5h of boiling maximum temperature, receive
Collect black liquor；Black liquor is heated to 60 DEG C of holding constant temperature in there-necked flask, is during which passed through nitrogen protection, acid adding adjusts the pH=of black liquor
3.Black liquor is cooled down, it is settled 3h after reacting, makes lignin/SiO in black liquor2Sedimentation is complete.Black liquor is centrifuged,
Rotating speed 8000r/min, centrifugation time 10min, supernatant liquor is poured out after centrifugation, is washed with deionized, according to aforesaid operations
Centrifuge again for several times, until pH is neutrality, it is lignin/SiO to collect lower floor's material2Compound.By lignin/SiO2Compound-
50 DEG C, be freeze-dried 36h under vacuum 10Pa, obtain lignin/SiO2Compound, it is ground with mortar to obtain powder.
(2) 2.0000g lignin/SiO is taken2Composite powder is put into Muffle furnace, introduces composite activating agent KOH and CO2Burn
Burn a period of time；KOH and lignin/SiO2The mass ratio of composite powder is 2：1, CO2Intake is 10L/min, calcination
Temperature is 500 DEG C, soak time 2h, and the micro- mesoporous activated carbon/SiO of nanometer is obtained after taking out cooling after arrival time2Composite wood
Material.
Embodiment 7
(1) it is raw material to weigh 500g straw, alkaline cooking, and alkali charge is relative to the 14% of over dry straw quality, anthraquinone phase
For the 0.1% of over dry straw quality, liquor ratio 1：5, heating-up time 2h, 155 DEG C, soaking time 0.5h of boiling maximum temperature, receive
Collect black liquor；Black liquor is heated to 60 DEG C of holding constant temperature in there-necked flask, is during which passed through nitrogen protection, acid adding adjusts the pH=of black liquor
3.Black liquor is cooled down, it is settled 3h after reacting, makes lignin/SiO in black liquor2Sedimentation is complete.Black liquor is centrifuged,
Rotating speed 8000r/min, centrifugation time 10min, supernatant liquor is poured out after centrifugation, is washed with deionized, according to aforesaid operations
Centrifuge again for several times, until pH is neutrality, it is lignin/SiO to collect lower floor's material2Compound.By lignin/SiO2Compound-
40 DEG C, be freeze-dried 24h under vacuum 2Pa, obtain lignin/SiO2Compound, it is ground with mortar to obtain powder.
(2) 2.0000g lignin/SiO is taken2Composite powder is put into Muffle furnace, introduces composite activating agent KOH and CO2Burn
Burn a period of time；KOH and lignin/SiO2The mass ratio of composite powder is 1：1, CO2Intake is 0.5L/min, calcination
Temperature be 600 DEG C, soak time 2h, after arrival time take out cooling after obtain the micro- mesoporous activated carbon/SiO of nanometer2It is compound
Material.
Fig. 2 is pore size distribution curve, it was confirmed that Product Activity charcoal is largely meso-hole structure and microcellular structure, average pore size
In 10nm, thus the product mainly with micropore and it is mesoporous based on, be a kind of micro- mesoporous material coexisted.
Embodiment 8：Micro- mesoporous activated carbon/the SiO of nanometer is prepared using black liquid2Composite iodine adsorption rate is tested
Micro- mesoporous activated carbon/the SiO of nanometer that embodiment 1~7 is prepared2The absorption property of composite is examined
Survey, it is as shown in table 1 with reference to the GBT12496.7-1990 wood activated charcoal iodine sorption value methods of inspection, three groups of test results.
Activated carbon/SiO of dries pulverizing under precise 1.0000g difference preparation conditions2Composite, it is placed in
50mL concentration is 0.1mol/L iodine standard solution.Put and filtered after vibrating 20min at 25 DEG C on the oscillator, take filter 10ml liquid
In iodine flask, titrated with 0.05mol/L sodium thiosulfate standard solutions when solution is presented faint yellow, add 2ml and form sediment
Powder indicator solution, lucky disappear of blueness for continuing to be titrated to solution is reaction end.The value of iodine absorption number is calculated as follows：
In formula：The iodine sorption value of K-sample, mg/g；
c1The concentration of-iodine standard solution, mol/L；
c2The concentration of-sodium thiosulfate standard solution, mol/L；
V2The dosage of-sodium thiosulfate standard solution, ml；
The quality of M-sample, g；
The molal weight of 127-iodine, g/mol.
Table 1. is a kind of to prepare the micro- mesoporous activated carbon/SiO of nanometer using black liquid2Composite iodine adsorption rate table
From table 1, when activation temperature reaches 600 DEG C, the absorption property of product reaches highest, with activation temperature after
There is downward trend in height of continuing rising, iodine adsorption rate.KOH and CO2It is used together as product prepared by synergistic catalyst than individually making
For catalyst when iodine sorption value it is all high, illustrate KOH and CO2It is obvious to be used in conjunction with synergy, can be used as synergistic catalyst.
Work as CO2When intake is 0.5L/min, the absorption property of product reaches highest, continues to increase with activator intake, iodine
Also there is downward trend in adsorption rate.Therefore, utilization black liquid optimal in the present invention prepares the micro- mesoporous activated carbon/SiO of nanometer2
It is 1 that the condition of composite, which is KOH relative to the mass ratio of lignin/silica composite,:1, CO2Intake is
0.5L/min, 600 DEG C of activation temperature, priming reaction time are 2h, and the iodine sorption value of product is 844mg/g.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. one kind prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2The method of composite, it is characterised in that including
Following steps：
(1) lignin/SiO is collected from black liquid2Compound, then by lignin/SiO2Compound is freeze-dried,
Crushed to obtain powder again；
(2) appropriate lignin/SiO is taken2Composite powder is put into Muffle furnace, introduces composite activating agent KOH and CO2, calcination is certain
Time obtains the micro- mesoporous activated carbon/SiO of nanometer after taking out cooling2Composite.
2. one kind according to claim 1 prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2The side of composite
Method, it is characterised in that step (1) the freeze-drying temperature is -10~-60 DEG C, and vacuum is 1.3~10Pa, the time 12
~48h.
3. one kind according to claim 1 prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2The side of composite
Method, it is characterised in that CO in the composite activating agent described in step (2)2Intake is 0.1-10.0L/min.
4. one kind according to claim 1 prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2The side of composite
Method, it is characterised in that KOH and lignin/SiO in the composite activating agent described in step (2)2Compound mass ratio for (0.5~
5)：1.
5. one kind according to claim 1 prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2The side of composite
Method, it is characterised in that the temperature of the calcination described in step (2) is 600~900 DEG C.
6. one kind according to claim 1 prepares the micro- mesoporous activated carbon/SiO of nanometer using black liquid2The side of composite
Method, it is characterised in that the time of the calcination described in step (2) is 1~5h.
A kind of 7. micro- mesoporous activated carbon/SiO of nanometer2Composite, it is characterised in that it is as described in any one of claim 1 to 6
One kind prepare nanometer micro- mesoporous activated carbon/SiO using black liquid2The method of composite is made.
8. the micro- mesoporous activated carbon/SiO of nanometer described in claim 72Composite is in environmental protection, medicine, military and chemical field
Application.
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Cited By (1)
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|---|---|---|---|---|
| CN108862274A (en) * | 2018-07-17 | 2018-11-23 | 华南理工大学 | A kind of preparation method and applications of cellulose base level porous carbon materials |
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| CN106167263A (en) * | 2016-08-21 | 2016-11-30 | 北京化工大学 | A kind of method using Lignin in Wastewater from Paper-Making Mill to prepare activated carbon |
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