CN108722356A - A kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite - Google Patents
A kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite Download PDFInfo
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- CN108722356A CN108722356A CN201810599359.3A CN201810599359A CN108722356A CN 108722356 A CN108722356 A CN 108722356A CN 201810599359 A CN201810599359 A CN 201810599359A CN 108722356 A CN108722356 A CN 108722356A
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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
- B01J20/28054—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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
A kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite, it is related to a kind of preparation method of hydrophilic porous biological carbon composite.It is of high cost the invention aims to solve the matrix of existing carrying metal particles, nano zero valence iron it is unstable it is easy reunite, remove the relatively low problem of performance during heavy metal using absorption.Method：One, biomass pyrolytic fused salt activates；Two, hydrophilic porous biological carbon materials are prepared；Three, nano zero valence iron is loaded, the hydrophilic porous biological carbon composite of nano zero valence iron load is obtained.The specific surface area that nano zero valence iron prepared by the present invention loads hydrophilic porous biological carbon composite can reach 603.4m2·g‑1.Since maize straw is agricultural wastes that are of low cost, deriving from a wealth of sources, it is pyrolyzed as basis material, reduces the cost of synthesis technology.The hydrophilic porous biological carbon composite of nano zero valence iron load prepared by the present invention repairs field for environmental contaminants.
Description
Technical field
The present invention relates to a kind of preparation methods of hydrophilic porous biological carbon composite.
Background technology
Nano zero valence iron is a kind of environmentally friendly material, has grain size small, and surface area is big, and reducing power is strong, reaction speed
Spend the advantages that fast.Therefore, nano zero valence iron is widely used in water remediation field.But since nano zero valence iron is deposited in air
Stability is poor, preserves that difficulty is big, easily in surrounding medium water or oxygen react, result in oxide layer to inhibit and pollutant
Further reaction.Further, since its surface energy is high, nano zero valence iron is easy to be condensed into larger particle, to reduce reaction
Activity, therefore, the utilization rate of nano zero valence iron are low.
In recent years, using the materials such as silica, polymer, clay mineral, activated carbon, graphene, carbon nanotube as
Carrier can effectively improve the stability of nano zero valence iron.But these above-mentioned carriers is of high cost, and adsorbed in application
Performance is relatively low during removing heavy metal.Studies have reported that, remove ground by using sepiolite supported extraction and nanometer iron metal
Heavy metal Pb in lower water2+, maximal absorptive capacity 44.05mg/g；Zero-valent Iron is supported on SiC nano-particles and is used for aqueous solution
Middle Pb2+Removal, which is 178.57mg/g to the maximal absorptive capacity of lead.
Invention content
It is of high cost the invention aims to solve the matrix of existing carrying metal particles, the unstable easy hair of nano zero valence iron
It is raw to reunite, using the relatively low problem of performance during absorption removal heavy metal, and provide a kind of nano zero valence iron load hydrophily
The preparation method of multiporous biological carbon composite.
A kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite, specifically according to the following steps
It completes：
One, biomass pyrolytic fused salt activates：
1., cutting crushing is carried out to charcoal raw material, reuse distilled water clean 5 times~10 times, then temperature be 70
DEG C~90 DEG C at it is dry, then dry charcoal raw material are sieved with 100 mesh sieve into~200 mesh sieve, obtain charcoal raw material fine powder；
2., charcoal raw material fine powder be ground with metal salt mix, obtain reactant；Reactant is placed in tubular type
In stove, it is passed through inert gas into tube furnace, tube furnace is warming up to 700 DEG C~900 DEG C under inert gas protection, then in temperature
Degree obtains the multiporous biological raw material of wood-charcoal after pyrolysis carbonization to be pyrolyzed 1h~3h under 700 DEG C~900 DEG C and inert gas atmosphere protection
Material；
Step 1 2. described in inert gas be nitrogen or argon gas；
Step 1 2. described in charcoal raw material fine powder and metal salt mass ratio be (1~10):1；
Two, 1., by the multiporous biological Carbon Materials after pyrolysis carbonization be placed in distilled water and clean, then will be after pyrolysis carbonization it is more
Hole biological carbon materials take out；
2., repeat step 2 1. 5 times~10 times, then at being 70 DEG C~90 DEG C in temperature it is dry, acid oxygen is immersed after dry
In agent solution, heating water bath 3h~for 24 hours further takes out, reuses distilled water flushing 5 times~10 times, then temperature be 70 DEG C~
It is dry at 90 DEG C, obtain hydrophilic porous biological carbon materials；
Three, under inert gas protection, hydrophilic porous biological carbon materials are dipped in molysite aqueous solution, low whipping speed
To stir 2h~10h under 1000r/min~1500r/min, it is constant to be kept stirring speed, and reducing solution is added dropwise, continues to stir
React 2h~10h, then centrifuge, then by the solid matter being centrifugally separating to obtain be 50 DEG C~70 DEG C in temperature at vacuum do
It is dry, obtain the hydrophilic porous biological carbon composite of nano zero valence iron load；
Inert gas described in step 3 is nitrogen or argon gas；
The mass ratio of molysite and reducing agent in reducing solution is 1 in molysite aqueous solution described in step 3:(0.1~
0.5)。
The principle of the present invention and advantage：
One, the present invention is combined with electronation using fused salt auxiliary and is prepared using charcoal raw material as raw material
Nano zero valence iron, which loads hydrophilic porous biological carbon composite, has larger specific surface area, nano zero-valence prepared by the present invention
The specific surface area that iron loads hydrophilic porous biological carbon composite can reach 603.4m2·g-1.And nano zero valence iron can
High uniformity is dispersed in hydrophilic porous biological carbon materials surface, therefore improves the utilization effect of nano zero valence iron in the environment
Rate；
Two, when the present invention mixes hydrophilic porous biological carbon materials with ferrous ion, hydrophilic porous biology raw material of wood-charcoal
Ferrous iron is adsorbed on its surface by the oxygen-containing functional group on material surface, is conducive to improve the nano zero valence iron generated in multiporous biological charcoal
The dispersion degree of material surface.The synergistic effect of nano zero valence iron and multiporous biological Carbon Materials improves its utilization effect in the environment
Rate；
Three, charcoal raw material are pyrolyzed as agricultural wastes cheap and easy to get and are used as basis material, reduce conjunction
At cost.And nano zero valence iron load is prepared in the method being combined with metal salt mixed pyrolysis, electronation using it
Hydrophilic porous biology carbon composite, is effectively improved the dispersion degree of nano zero valence iron, improves it and is led in environment remediation
The utility value in domain；
Four, the hydrophilic porous biological carbon composite of nano zero valence iron load that prepared by the present invention removes heavy metal Pb2+'s
Adsorbance is 174.5mgg-1~195.0mgg-1；Remove heavy metal Cu2+Adsorbance be 68.8mgg-1~
161.9mg·g-1, remove heavy metal Zn2+Adsorbance be 62.1mgg-1~109.7mgg-1；
Five, preparation method of the present invention is easy, and raw material is cheap and easy to get, therefore is suitble to large batch of be synthetically prepared.
The hydrophilic porous biological carbon composite of nano zero valence iron load prepared by the present invention is used for environmental contaminants reparation
Field.
Description of the drawings
Fig. 1 is the scanning that nano zero valence iron prepared by one step 3 of embodiment loads hydrophilic porous biological carbon composite
Electron microscope；
Fig. 2 is the transmission that nano zero valence iron prepared by one step 3 of embodiment loads hydrophilic porous biological carbon composite
Electron microscope；
Fig. 3 is the XRD that nano zero valence iron prepared by one step 3 of embodiment loads hydrophilic porous biological carbon composite
Spectrogram；
Fig. 4 is the N that nano zero valence iron prepared by one step 3 of embodiment loads hydrophilic porous biological carbon composite2It inhales
Attached-desorption spectrogram.
Specific implementation mode
Technical solution of the present invention is not limited to act specific implementation mode set forth below, further includes between each specific implementation mode
Arbitrary combination.
Specific implementation mode one：Present embodiment is a kind of hydrophilic porous biological carbon composite of nano zero valence iron load
Preparation method, be specifically realized by the following steps：
One, biomass pyrolytic fused salt activates：
1., cutting crushing is carried out to charcoal raw material, reuse distilled water clean 5 times~10 times, then temperature be 70
DEG C~90 DEG C at it is dry, then dry charcoal raw material are sieved with 100 mesh sieve into~200 mesh sieve, obtain charcoal raw material fine powder；
2., charcoal raw material fine powder be ground with metal salt mix, obtain reactant；Reactant is placed in tubular type
In stove, it is passed through inert gas into tube furnace, tube furnace is warming up to 700 DEG C~900 DEG C under inert gas protection, then in temperature
Degree obtains the multiporous biological raw material of wood-charcoal after pyrolysis carbonization to be pyrolyzed 1h~3h under 700 DEG C~900 DEG C and inert gas atmosphere protection
Material；
Step 1 2. described in inert gas be nitrogen or argon gas；
Step 1 2. described in charcoal raw material fine powder and metal salt mass ratio be (1~10):1；
Two, 1., by the multiporous biological Carbon Materials after pyrolysis carbonization be placed in distilled water and clean, then will be after pyrolysis carbonization it is more
Hole biological carbon materials take out；
2., repeat step 2 1. 5 times~10 times, then at being 70 DEG C~90 DEG C in temperature it is dry, acid oxygen is immersed after dry
In agent solution, heating water bath 3h~for 24 hours further takes out, reuses distilled water flushing 5 times~10 times, then temperature be 70 DEG C~
It is dry at 90 DEG C, obtain hydrophilic porous biological carbon materials；
Three, under inert gas protection, hydrophilic porous biological carbon materials are dipped in molysite aqueous solution, low whipping speed
To stir 2h~10h under 1000r/min~1500r/min, it is constant to be kept stirring speed, and reducing solution is added dropwise, continues to stir
React 2h~10h, then centrifuge, then by the solid matter being centrifugally separating to obtain be 50 DEG C~70 DEG C in temperature at vacuum do
It is dry, obtain the hydrophilic porous biological carbon composite of nano zero valence iron load；
Inert gas described in step 3 is nitrogen or argon gas；
The mass ratio of molysite and reducing agent in reducing solution is 1 in molysite aqueous solution described in step 3:(0.1~
0.5)。
2. purpose that present embodiment step 1 is pyrolyzed is：Metal salt fusing is to activated biomass under high temperature, with
Multiporous biological charcoal is prepared, the multiporous biological Carbon Materials obtained after pyrolysis have apparent graded porous structure.
It is more to enhance by the way that multiporous biological Carbon Materials are immersed in acidic oxidation agent solution in present embodiment step 2
The hydrophily ability of hole biological carbon materials so that multiporous biological Carbon Materials can be preferably soluble in water；And pass through this process
Processing can improve the oxygen-containing functional group number of multiporous biological charcoal material surface, be conducive to the application range for increasing its material.
The purpose of dropwise addition reducing solution is in present embodiment step 3：Make to be adsorbed on hydrophilic porous biological carbon materials
The ferrous iron in-situ reducing on surface is Zero-valent Iron, and restores obtained nano zero valence iron and be highly dispersed at hydrophilic porous biology
Charcoal material surface.
The principle and advantage of present embodiment：
One, present embodiment is combined with electronation using fused salt auxiliary and is prepared into using charcoal raw material as raw material
To nano zero valence iron load hydrophilic porous biological carbon composite there is larger specific surface area, prepared by present embodiment
The specific surface area that nano zero valence iron loads hydrophilic porous biological carbon composite can reach 603.4m2·g-1.And nanometer zero
Valence iron can high uniformity be dispersed in hydrophilic porous biological carbon materials surface, therefore improve nano zero valence iron in the environment
Utilization ratio；
Two, when present embodiment mixes hydrophilic porous biological carbon materials with ferrous ion, hydrophilic porous biology
Ferrous iron is adsorbed on its surface by the oxygen-containing functional group of charcoal material surface, is conducive to improve the nano zero valence iron generated in porous life
The dispersion degree of object charcoal material surface.The synergistic effect of nano zero valence iron and multiporous biological Carbon Materials improves its profit in the environment
Use efficiency；
Three, charcoal raw material are pyrolyzed as agricultural wastes cheap and easy to get and are used as basis material, reduce conjunction
At cost.And nano zero valence iron load is prepared in the method being combined with metal salt mixed pyrolysis, electronation using it
Hydrophilic porous biology carbon composite, is effectively improved the dispersion degree of nano zero valence iron, improves it and is led in environment remediation
The utility value in domain；
Four, present embodiment preparation method is easy, and raw material is cheap and easy to get, therefore is suitble to large batch of be synthetically prepared.
The hydrophilic porous biological carbon composite of nano zero valence iron load prepared by present embodiment is used for environmental contaminants
Reparation field.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：Step 1 1. described in life
Object charcoal raw material are one kind or in which several mixing in maize straw, wheat stalk, soybean stalk, rice straw and rice husk
Object.It is other same as the specific embodiment one.
Specific implementation mode three：The present embodiment is different from the first and the second embodiment in that：Step 1 2. described in
Metal salt be KHCO3Or NaHCO3.It is other the same as one or two specific embodiments.
Specific implementation mode four：Unlike one of present embodiment and specific implementation mode one to three：Step 1 2. in
Heating rate when tube furnace is warming up to 700 DEG C~900 DEG C is 8 DEG C/min~11 DEG C/min.Other and specific implementation mode one
It is identical to one of three.
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode one to four：Step 1 2. in
Charcoal raw material fine powder is ground with metal salt and is mixed, reactant is obtained；Reactant is placed in tube furnace, to tubular type
Be passed through inert gas in stove, tube furnace be warming up to 700 DEG C~800 DEG C under inert gas protection, then temperature be 700 DEG C~
800 DEG C and the lower pyrolysis 1h~2h of inert gas atmosphere protection, obtain the multiporous biological Carbon Materials after pyrolysis carbonization.It is other with it is specific
One of embodiment one to four is identical.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode one to five：Step 1 2. in
The mass ratio of the charcoal raw material fine powder and metal salt is (1~5):1.One of other and specific implementation mode one to five
It is identical.
Specific implementation mode seven：Unlike one of present embodiment and specific implementation mode one to six：Step 2 2. in
The temperature of the heating water bath is 50 DEG C~70 DEG C.It is other identical as one of specific implementation mode one to six.
Specific implementation mode eight：Unlike one of present embodiment and specific implementation mode one to seven：Step 2 2. in
The acidic oxidation agent solution is (NH4)2S2O8The mixed liquor that the sulfuric acid for being 10%~20% with mass fraction forms；It is described
Acidic oxidation agent solution in (NH4)2S2O8And H2SO4Molar ratio be 1:(1~5).Other and specific implementation mode one to seven
One of it is identical.
Specific implementation mode nine：Unlike one of present embodiment and specific implementation mode one to eight：Institute in step 3
The molysite aqueous solution stated is ferrous nitrate, ferrous sulfate solution or frerrous chloride, a concentration of 0.02molL of molysite aqueous solution-1
~0.2molL-1.It is other identical as one of specific implementation mode one to eight.
Specific implementation mode ten：Unlike one of present embodiment and specific implementation mode one to nine：Institute in step 3
The reducing solution stated is NaBH4Solution, a concentration of 0.1molL of reducing solution-1~1molL-1。
It is other identical as one of specific implementation mode one to nine.
Elaborate below to the embodiment of the present invention, following embodiment under based on the technical solution of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment one：A kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite, specifically
It completes according to the following steps：
One, biomass pyrolytic fused salt activates：
1., cutting crushing is carried out to charcoal raw material, reuse distilled water clean 7 times, then temperature be 80 DEG C at do
It is dry, then dry charcoal raw material are sieved with 100 mesh sieve, obtain charcoal raw material fine powder；
Step 1 1. described in charcoal raw material be maize straw；
2., charcoal raw material fine powder be ground with metal salt mix, obtain reactant；Reactant is placed in tubular type
In stove, it is passed through nitrogen into tube furnace, tube furnace is warming up to 800 DEG C under nitrogen protection, then in temperature is 800 DEG C and nitrogen
It is pyrolyzed 2h under atmosphere protection, obtains the multiporous biological Carbon Materials after pyrolysis carbonization；
Step 1 2. described in metal salt be KHCO3；
Step 1 2. described in charcoal raw material fine powder and metal salt mass ratio be 1:1；
Step 1 2. in heating rate of tube furnace when being warming up to 800 DEG C be 10 DEG C/min；
Two, 1., by the multiporous biological Carbon Materials after pyrolysis carbonization be placed in distilled water and clean, then will be after pyrolysis carbonization it is more
Hole biological carbon materials take out；
2., repeat step 2 1. 7 times, then at being 80 DEG C in temperature it is dry, immersed in acidic oxidation agent solution after dry, water
Bath heating 8h, further takes out, reuses distilled water flushing 7 times, then is dried at being 80 DEG C in temperature, obtains hydrophilic porous charcoal
Material；
Step 2 2. described in heating water bath temperature be 60 DEG C；
Step 2 2. described in acidic oxidation agent solution be (NH4)2S2O8The sulfuric acid for being 17.5% with mass fraction forms
Mixed liquor；(NH in the acidic oxidation agent solution4)2S2O8And H2SO4Molar ratio be 1:2；
Three, under inert gas protection, hydrophilic porous biological carbon materials are dipped in molysite aqueous solution, low whipping speed
To stir 4h under 1200r/min, it is constant to be kept stirring speed, and reducing solution is added dropwise, continues to be stirred to react 5h, then centrifuges point
From, then by the solid matter being centrifugally separating to obtain temperature be 60 DEG C at be dried in vacuo, obtain nano zero valence iron load hydrophily
Multiporous biological carbon composite；
Inert gas described in step 3 is nitrogen；
Molysite aqueous solution described in step 3 is ferrous sulfate solution, a concentration of 0.075molL of molysite aqueous solution-1；
Reducing solution described in step 3 is NaBH4Solution, a concentration of 0.3molL of reducing solution-1；
The mass ratio of molysite and reducing agent in reducing solution is 1 in molysite aqueous solution described in step 3:0.27.
Nano zero-valence in the hydrophilic porous biological carbon composite of nano zero valence iron load prepared by one step 3 of embodiment
The mass ratio of iron and hydrophilic porous biological carbon materials is 1:1.
Nano zero valence iron prepared by one step 3 of embodiment loads the scanning electron microscope of hydrophilic porous biological carbon composite
Photo is as shown in Figure 1；
Nano zero valence iron prepared by one step 3 of embodiment loads the transmission electron microscope of hydrophilic porous biological carbon composite
Photo is as shown in Figure 2.
Fig. 1 is the scanning that nano zero valence iron prepared by one step 3 of embodiment loads hydrophilic porous biological carbon composite
Electron microscope；
From fig. 1, it can be seen that nanometer nulvalent iron particle is dispersed in the surface of hydrophilic porous biological carbon materials.
Fig. 2 is the transmission that nano zero valence iron prepared by one step 3 of embodiment loads hydrophilic porous biological carbon composite
Electron microscope；
As can be seen from Figure 2, nanometer nulvalent iron particle soilless sticking phenomenon, average grain diameter is in 100nm or so and is dispersed in parent
The surface of aqueous multiporous biological Carbon Materials；
Fig. 3 is the XRD that nano zero valence iron prepared by one step 3 of embodiment loads hydrophilic porous biological carbon composite
Spectrogram；
The hydrophilic porous charcoal of nano zero valence iron load that the preparation of one step 3 of embodiment can be analyzed to obtain from Fig. 3 is multiple
The crystalline nature of condensation material.In XRD spectrum by 21.6 ° centered on wide and weak diffraction maximum be attributed to carbon and mainly with
Amorphous form exists.Three strong 44.7 °, 65.0 ° and 82.3 ° of diffraction maximum is showed in sample, corresponds respectively to nano zero-valence
Iron (Fe0) (JCPDS, NO.87-0721)) and (100), (200) and (211) crystal face.These the result shows that well-crystallized nanometer
Zero-valent Iron has successfully been supported on the surface of hydrophilic porous biological carbon materials.
Fig. 4 is the N that nano zero valence iron prepared by one step 3 of embodiment loads hydrophilic porous biological carbon composite2It inhales
Attached-desorption spectrogram.
From fig. 4, it can be seen that the hydrophilic porous charcoal of nano zero valence iron load prepared by one step 3 of embodiment is compound
Material has the isothermal feature of II types, (P/P under medium relative pressure0=0.4-0.95) by capillary condensation generation, there are H4
Type hysteresis loop shows that there are micro- for the hydrophilic porous biological carbon composite of the nano zero valence iron load of one step 3 of embodiment preparation
Hole and central hole structure.
Nano zero valence iron prepared by one step 3 of embodiment loads the specific surface area of hydrophilic porous biological carbon composite
Up to 603.4m2·g-1。
Embodiment two：A kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite, specifically
It completes according to the following steps：
One, biomass pyrolytic fused salt activates：
1., cutting crushing is carried out to charcoal raw material, reuse distilled water clean 7 times, then temperature be 80 DEG C at do
It is dry, then dry charcoal raw material are sieved with 100 mesh sieve, obtain charcoal raw material fine powder；
Step 1 1. described in charcoal raw material be maize straw；
2., charcoal raw material fine powder be ground with metal salt mix, obtain reactant；Reactant is placed in tubular type
In stove, it is passed through nitrogen into tube furnace, tube furnace is warming up to 800 DEG C under nitrogen protection, then in temperature is 800 DEG C and nitrogen
It is pyrolyzed 2h under atmosphere protection, obtains the multiporous biological Carbon Materials after pyrolysis carbonization；
Step 1 2. described in metal salt be KHCO3；
Step 1 2. described in charcoal raw material fine powder and metal salt mass ratio be 1:1；
Step 1 2. in heating rate of tube furnace when being warming up to 800 DEG C be 10 DEG C/min；
Two, 1., by the multiporous biological Carbon Materials after pyrolysis carbonization be placed in distilled water and clean, then will be after pyrolysis carbonization it is more
Hole biological carbon materials take out；
2., repeat step 2 1. 7 times, then at being 80 DEG C in temperature it is dry, immersed in acidic oxidation agent solution after dry, water
Bath heating 8h, further takes out, reuses distilled water flushing 7 times, then is dried at being 80 DEG C in temperature, obtains hydrophilic porous charcoal
Material；
Step 2 2. described in heating water bath temperature be 60 DEG C；
Step 2 2. described in acidic oxidation agent solution be (NH4)2S2O8The sulfuric acid for being 17.5% with mass fraction forms
Mixed liquor；(NH in the acidic oxidation agent solution4)2S2O8And H2SO4Molar ratio be 1:2；
Three, under inert gas protection, hydrophilic porous biological carbon materials are dipped in molysite aqueous solution, low whipping speed
To stir 4h under 1200r/min, it is constant to be kept stirring speed, and reducing solution is added dropwise, continues to be stirred to react 5h, then centrifuges point
From, then by the solid matter being centrifugally separating to obtain temperature be 60 DEG C at be dried in vacuo, obtain nano zero valence iron load hydrophily
Multiporous biological carbon composite；
Inert gas described in step 3 is nitrogen；
Molysite aqueous solution described in step 3 is ferrous sulfate solution, a concentration of 0.035molL of molysite aqueous solution-1；
Reducing solution described in step 3 is NaBH4Solution, a concentration of 0.15molL of reducing solution-1；
The mass ratio of molysite and reducing agent in reducing solution is 1 in molysite aqueous solution described in step 3:0.27.
Nano zero-valence in the hydrophilic porous biological carbon composite of nano zero valence iron load prepared by two step 3 of embodiment
The mass ratio of iron and hydrophilic porous biological carbon materials is 1:2.
Embodiment three：A kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite, specifically
It completes according to the following steps：
One, biomass pyrolytic fused salt activates：
1., cutting crushing is carried out to charcoal raw material, reuse distilled water clean 7 times, then temperature be 80 DEG C at do
It is dry, then dry charcoal raw material are sieved with 100 mesh sieve, obtain charcoal raw material fine powder；
Step 1 1. described in charcoal raw material be maize straw；
2., charcoal raw material fine powder be ground with metal salt mix, obtain reactant；Reactant is placed in tubular type
In stove, it is passed through nitrogen into tube furnace, tube furnace is warming up to 800 DEG C under nitrogen protection, then in temperature is 800 DEG C and nitrogen
It is pyrolyzed 2h under atmosphere protection, obtains the multiporous biological Carbon Materials after pyrolysis carbonization；
Step 1 2. described in metal salt be KHCO3；
Step 1 2. described in charcoal raw material fine powder and metal salt mass ratio be 1:1；
Step 1 2. in heating rate of tube furnace when being warming up to 800 DEG C be 10 DEG C/min；
Two, 1., by the multiporous biological Carbon Materials after pyrolysis carbonization be placed in distilled water and clean, then will be after pyrolysis carbonization it is more
Hole biological carbon materials take out；
2., repeat step 2 1. 7 times, then at being 80 DEG C in temperature it is dry, immersed in acidic oxidation agent solution after dry, water
Bath heating 8h, further takes out, reuses distilled water flushing 7 times, then is dried at being 80 DEG C in temperature, obtains hydrophilic porous charcoal
Material；
Step 2 2. described in heating water bath temperature be 60 DEG C；
Step 2 2. described in acidic oxidation agent solution be (NH4)2S2O8The sulfuric acid for being 17.5% with mass fraction forms
Mixed liquor；(NH in the acidic oxidation agent solution4)2S2O8And H2SO4Molar ratio be 1:2；
Three, under inert gas protection, hydrophilic porous biological carbon materials are dipped in molysite aqueous solution, low whipping speed
To stir 4h under 1200r/min, it is constant to be kept stirring speed, and reducing solution is added dropwise, continues to be stirred to react 5h, then centrifuges point
From, then by the solid matter being centrifugally separating to obtain temperature be 60 DEG C at be dried in vacuo, obtain nano zero valence iron load hydrophily
Multiporous biological carbon composite；
Inert gas described in step 3 is nitrogen；
Molysite aqueous solution described in step 3 is ferrous sulfate solution, a concentration of 0.15molL of molysite aqueous solution-1；
Reducing solution described in step 3 is NaBH4Solution, a concentration of 0.6molL of reducing solution-1；
The mass ratio of molysite and reducing agent in reducing solution is 1 in molysite aqueous solution described in step 3:0.27.
Nano zero-valence in the hydrophilic porous biological carbon composite of nano zero valence iron load prepared by three step 3 of embodiment
The mass ratio of iron and hydrophilic porous biological carbon materials is 2:1.
The hydrophilic porous biological carbon composite of nano zero valence iron load prepared by one step 3 of embodiment removes heavy metal
Pb2+、Cu2+And Zn2+, adsorbance respectively is 192.8mgg-1, 125.4mgg-1And 73.8mgg-1, and use real
Apply the multiporous biological Carbon Materials absorption heavy metal Pb after 2. pyrolysis carbonization that one step 1 of example obtains2+、Cu2+And Zn2+, adsorbance
It respectively is 108.1mgg-1, 50.8mgg-1And 33.5mgg-1, adsorption effect be substantially less than one step of embodiment
The three hydrophilic porous biological carbon composites of nano zero valence iron load prepared.
The hydrophilic porous biological carbon composite of nano zero valence iron load prepared by two step 3 of embodiment removes heavy metal
Pb2+、Cu2+And Zn2+, adsorbance respectively is 174.5mgg-1, 68.8mgg-1And 62.1mgg-1。
The hydrophilic porous biological carbon composite of nano zero valence iron load prepared by three step 3 of embodiment removes heavy metal
Pb2+、Cu2+And Zn2+, adsorbance respectively is 195.0mgg-1, 161.9mgg-1And 109.7mgg-1。
Claims (10)
1. a kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite, it is characterised in that a kind of nanometer
Zero-valent Iron loads what the preparation method of hydrophilic porous biological carbon composite was specifically realized by the following steps：
One, biomass pyrolytic fused salt activates：
1., cutting crushing is carried out to charcoal raw material, reuse distilled water clean 5 times~10 times, then temperature be 70 DEG C~
It is dry at 90 DEG C, then dry charcoal raw material are sieved with 100 mesh sieve into~200 mesh sieve, obtain charcoal raw material fine powder；
2., charcoal raw material fine powder be ground with metal salt mix, obtain reactant；Reactant is placed in tube furnace
In, it is passed through inert gas into tube furnace, tube furnace is warming up to 700 DEG C~900 DEG C under inert gas protection, then in temperature
For 700 DEG C~900 DEG C and the lower pyrolysis 1h~3h of inert gas atmosphere protection, the multiporous biological Carbon Materials after pyrolysis carbonization are obtained；
Step 1 2. described in inert gas be nitrogen or argon gas；
Step 1 2. described in charcoal raw material fine powder and metal salt mass ratio be (1~10):1；
Two, it 1., by the multiporous biological Carbon Materials after pyrolysis carbonization is placed in distilled water and cleans, then by the porous life after pyrolysis carbonization
Object Carbon Materials take out；
2., repeat step 2 1. 5 times~10 times, then at being 70 DEG C~90 DEG C in temperature it is dry, immerse acidic oxidation agent after dry
In solution, heating water bath 3h~for 24 hours further takes out, reuses distilled water flushing 5 times~10 times, then in temperature is 70 DEG C~90 DEG C
Lower drying, obtains hydrophilic porous biological carbon materials；
Three, under inert gas protection, hydrophilic porous biological carbon materials are dipped in molysite aqueous solution, low whipping speed is
2h~10h is stirred under 1000r/min~1500r/min, it is constant to be kept stirring speed, and reducing solution is added dropwise, and it is anti-to continue stirring
Answer 2h~10h, then centrifuge, then by the solid matter being centrifugally separating to obtain temperature be 50 DEG C~70 DEG C at be dried in vacuo,
Obtain the hydrophilic porous biological carbon composite of nano zero valence iron load；
Inert gas described in step 3 is nitrogen or argon gas；
The mass ratio of molysite and reducing agent in reducing solution is 1 in molysite aqueous solution described in step 3:(0.1~0.5).
2. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that step 1 1. described in charcoal raw material be maize straw, wheat stalk, soybean stalk, rice straw
One kind in stalk and rice husk or in which several mixtures.
3. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that step 1 2. described in metal salt be KHCO3Or NaHCO3。
4. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that step 1 2. in heating rate of tube furnace when being warming up to 700 DEG C~900 DEG C be 8 DEG C/min~11 DEG C/
min。
5. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that step 1 2. in charcoal raw material fine powder be ground with metal salt mix, obtain reactant；It will be anti-
Answer object to be placed in tube furnace, inert gas be passed through into tube furnace, under inert gas protection by tube furnace be warming up to 700 DEG C~
800 DEG C, then it is pyrolyzed 1h~2h under being 700 DEG C~800 DEG C and inert gas atmosphere protection in temperature, it obtains more after pyrolysis carbonization
Hole biological carbon materials.
6. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that step 1 2. described in charcoal raw material fine powder and metal salt mass ratio be (1~5):1.
7. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that step 2 2. described in heating water bath temperature be 50 DEG C~70 DEG C.
8. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that step 2 2. described in acidic oxidation agent solution be (NH4)2S2O8It is 10%~20% with mass fraction
Sulfuric acid composition mixed liquor；(NH in the acidic oxidation agent solution4)2S2O8And H2SO4Molar ratio be 1:(1~5).
9. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that the molysite aqueous solution described in step 3 is ferrous nitrate, ferrous sulfate solution or frerrous chloride, molysite water
A concentration of 0.02molL of solution-1~0.2molL-1。
10. a kind of nano zero valence iron according to claim 1 loads the preparation side of hydrophilic porous biological carbon composite
Method, it is characterised in that the reducing solution described in step 3 is NaBH4Solution, a concentration of 0.1molL of reducing solution-1
~1molL-1。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148014A (en) * | 2014-07-30 | 2014-11-19 | 华南理工大学 | High-water-absorbing carbon material under low-humidity condition and modification and preparation method thereof |
| CN106745645A (en) * | 2016-12-20 | 2017-05-31 | 山西省环境科学研究院 | The preparation method and applications of nano zero-valence iron composite material |
| CN107930629A (en) * | 2017-11-15 | 2018-04-20 | 南京理工大学 | The preparation method of support type charcoal catalysis material |
-
2018
- 2018-06-11 CN CN201810599359.3A patent/CN108722356B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148014A (en) * | 2014-07-30 | 2014-11-19 | 华南理工大学 | High-water-absorbing carbon material under low-humidity condition and modification and preparation method thereof |
| CN106745645A (en) * | 2016-12-20 | 2017-05-31 | 山西省环境科学研究院 | The preparation method and applications of nano zero-valence iron composite material |
| CN107930629A (en) * | 2017-11-15 | 2018-04-20 | 南京理工大学 | The preparation method of support type charcoal catalysis material |
Non-Patent Citations (1)
| Title |
|---|
| 薛智勇: "《农业固体废物处理与处置》", 30 November 2016 * |
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