CN107081137B - Lignin graft bentonite loads nano zero valence iron composite material and preparation method - Google Patents

Lignin graft bentonite loads nano zero valence iron composite material and preparation method Download PDF

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CN107081137B
CN107081137B CN201710240177.2A CN201710240177A CN107081137B CN 107081137 B CN107081137 B CN 107081137B CN 201710240177 A CN201710240177 A CN 201710240177A CN 107081137 B CN107081137 B CN 107081137B
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lignin
composite material
nano zero
valence iron
bentonite
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CN107081137A (en
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王振
迟泽旭
楚焕庆
刘玉
杨桂花
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Qilu University of Technology
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • 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
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a kind of lignin graft bentonites to load nano zero valence iron composite material and preparation method, belongs to technical field of function materials.The characteristics of composite material, is grafted lignin and bentonite to load nano zero valence iron.Compared with prior art, the dispersibility and stability of nano zero valence iron are obviously improved in composite material of the present invention, have good waste treatment capacity, have good application value.

Description

Lignin graft bentonite loads nano zero valence iron composite material and preparation method
Technical field
The present invention relates to technical field of function materials, specifically a kind of lignin graft bentonite loads nano zero-valence Iron composite material and preparation method thereof.
Background technique
Nano zero-valence iron particle in removing polluted-water certain organic matters and the problems such as other environment remediations on show Excellent physical and chemical performance.But since nano zero-valence iron particle itself has magnetism, and the method system that activity is very high, current Standby nulvalent iron particle easily reacts or is reunited with surrounding medium, forms biggish wadding body, leads to active reduction, extremely unfavorable In the repair of environmental pollution.Therefore, Fe is improved0Degree of scatter for improve its activity and efficiency be vital.
Bentonite has the heavy metal in very big potential removal waste water as a kind of cheap, efficient adsorbent.Swelling Soil has good chemistry and mechanical property, preferable absorption property and unique interlayer structure.
The document that alta-mud loaded nano Zero-valent Iron is applied to sewage treatment is disclosed although having in the prior art, only That nano zero valence iron is simply loaded into bentonite surface, in sewage disposal process mainly be utilized it is bentonitic absorption and The strong reducing action of nano zero valence iron, is adsorbed in bentonite surface for polluter first, and subsequent nano zero valence iron can will pollute Substance carries out deoxidization, degradation, although the method can reduce the reunion of nano zero valence iron, but still has agglomeration, and in reality Nano zero valence iron is easily oxidized in sewage disposal process, greatly reduces service efficiency, keeps treatment effect undesirable, and be applicable in Range is relatively narrow, is not suitable for COD and the higher sewage of coloration.
Lignin is as a kind of valuable biomass resource, not only rich reserves, but also cheap, has Every physical and chemical performance causes all circles widely to be studied already, and higher value application how is carried out to it becomes the hot spot studied at present.
Summary of the invention
Technical assignment of the invention is in view of the above shortcomings of the prior art, to provide a kind of with good dispersion and stabilization Property lignin graft bentonite load nano zero-valence iron composite material.
The further technical assignment of the present invention is to provide the preparation method of above-mentioned composite material.
Technical assignment of the invention is realized in the following manner: it is compound that lignin graft bentonite loads nano zero valence iron Material, its main feature is that lignin and bentonite are grafted to load nano zero valence iron.
Preferably, above-mentioned composite material is made by following methods:
S1. bentonite and lignin are added in ferric trichloride or ferrous sulfate aqueous solution under inert gas shielding, and acute It is strong to stir to get mixed liquor；
S2. successively by sodium borohydride aqueous solution, acrylamide aqueous solution and N, N'- methylene-bisacrylamide aqueous solution adds Enter in mixed liquor, initiator is added after stirring；
S3. after the reaction was completed, separate, purification is dried in vacuo to obtain composite material target product.
In order to keep lytic activity for a long time, the composite material being dried in vacuo can save in an inert atmosphere It is spare.
Preferably, the mass ratio of lignin, bentonite and ferro element is 1:(0.5~1.5): (0.5~1.5), most preferably Mass ratio is 1:(0.8~1.2): (0.8~1.2).
The mass ratio of lignin and acrylamide is preferably 1:(1.0~5.0), most preferably 1:(1.0~2.0).
Lignin and N, the mass ratio of N'- methylene-bisacrylamide are preferably 1:(0.1~0.75), most preferably 1:(0.1 ~0.2).
The initiator is preferably potassium peroxydisulfate and N, N, N, N- tetramethylethylenediamine, wherein lignin and potassium peroxydisulfate Mass ratio be 1:(0.1~0.75), preferably 1:(0.1~0.25)；Lignin and N, N, N, the matter of N- tetramethylethylenediamine Amount is than being 1:(0.02~0.05), most preferably 1:0.03~0.04.
Above-mentioned lignin graft bentonite load nano zero-valence iron composite material is made preferably at 25~60 DEG C, best anti- Answering temperature is 25~30 DEG C.Reaction time is 0.5~4 hour, preferably 1-2 hours.
Lignin graft bentonite load nano zero valence iron composite material and preparation method of the invention and the prior art Compared to following prominent the utility model has the advantages that
(1) present invention states nano zero-valence in lignin graft bentonite load nano zero-valence iron composite material (BL-nZVI) The dispersibility and stability of iron are obviously improved；
(2) using resourceful cheap lignin as primary raw material, new way is provided for the higher value application of lignin Diameter.Have much the functional group that can participate in a variety of chemical reactions on the structural unit and side chain of lignin, as hydroxyl (alcoholic extract hydroxyl group and Phenolic hydroxyl group), carbonyl, aromatic radical, methoxyl group, double bond etc., be advantageously implemented and bentonitic grafting；
(3) lignin graft bentonite load nano zero-valence iron composite material (BL-nZVI) of the present invention, both had The preferable adsorption capacity of bentonite, but the tridimensional network and the various active functional group that take full advantage of lignin complexity are steady Fixed and dispersion nano zero valence iron, can effectively prevent the oxidation of nano zero valence iron, have good treatment effect to paper waste.
Detailed description of the invention
Attached drawing 1 is that lignin graft bentonite prepared by embodiment 3 loads nano zero-valence iron composite material (BL-nZVI) With the scanning electron microscope comparison diagram of nano zero valence iron (nZVI) and alta-mud loaded nano Zero-valent Iron (B-nZVI), a is nano zero-valence Iron (nZVI), b are alta-mud loaded nano Zero-valent Iron (B-nZVI), and c is that lignin graft bentonite loads nano zero valence iron (BL-nZVI)。
Attached drawing 2 is that lignin graft bentonite prepared by embodiment 3 loads nano zero-valence iron composite material (BL-nZVI) With the infrared and XRD comparison diagram of nano zero valence iron (nZVI) and alta-mud loaded nano Zero-valent Iron (B-nZVI).
Attached drawing 3 is the comparison diagram of experimental example COD removal rate.
Specific embodiment
It is multiple to lignin graft bentonite load nano zero valence iron of the invention with specific embodiment referring to Figure of description Condensation material and preparation method thereof is described in detail below.
Unless otherwise instructed, the content of following each ingredients used is weight percentage content.
[embodiment 1]
At 25 DEG C, 9.66g ferric trichloride is dissolved in 50ml distilled water, three-necked flask is transferred to, leads to nitrogen, stirring.With 2g bentonite is added in backward three-necked flask, 2g lignin is vigorously stirred 30 minutes.After stirring, by 3.54g sodium borohydride It is dissolved in 100ml distilled water, is added in three-necked flask with the speed of 1-2 drop per second, after being added dropwise, is stirred 10 minutes.Then 2g acrylamide is dissolved in 10ml distilled water, 0.4gN, N'- methylene-bisacrylamide is dissolved in 20ml distilled water, is successively added to In three-necked flask, stir 30 minutes.After stirring, 0.2g potassium peroxydisulfate is dissolved in 10ml distilled water, is added in three-necked flask, And the N, N, N of 100 microlitres of addition, N- tetramethylethylenediamine stir 30 minutes.Product vacuum filtration, and three times with ethanol washing, Subsequent 30 degrees Celsius are dried in vacuum overnight, and after dry, product taking-up are put into hermetic bag, inflated with nitrogen saves backup.
[embodiment 2]
At 30 DEG C, 9.66g ferric trichloride is dissolved in 50ml distilled water, three-necked flask is transferred to, leads to nitrogen, stirring.With 2g bentonite is added in backward three-necked flask, 2g lignin is vigorously stirred 30 minutes.After stirring, by 3.54g sodium borohydride It is dissolved in 100ml distilled water, is added in three-necked flask with the speed of 1-2 drop per second, after being added dropwise, is stirred 10 minutes.Then 3g acrylamide is dissolved in 10ml distilled water, 0.3gN, N'- methylene-bisacrylamide is dissolved in 20ml distilled water, is successively added to In three-necked flask, stir 30 minutes.After stirring, 0.3g potassium peroxydisulfate is dissolved in 10ml distilled water, is added in three-necked flask, And the N, N, N of 100 microlitres of addition, N- tetramethylethylenediamine stir 30 minutes.Product vacuum filtration, and three times with ethanol washing, Subsequent 30 degrees Celsius are dried in vacuum overnight, and after dry, product taking-up are put into hermetic bag, inflated with nitrogen saves backup.
[embodiment 3]
At 30 DEG C, 9.66g ferric trichloride is dissolved in 50ml distilled water, three-necked flask is transferred to, leads to nitrogen, stirring.With 2g bentonite is added in backward three-necked flask, 2g lignin is vigorously stirred 30 minutes.After stirring, by 3.54g sodium borohydride It is dissolved in 100ml distilled water, is added in three-necked flask with the speed of 1-2 drop per second, after being added dropwise, is stirred 10 minutes.Then 4g acrylamide is dissolved in 10ml distilled water, 0.2g N, N'- methylene-bisacrylamide is dissolved in 20ml distilled water, is successively added Into three-necked flask, stir 30 minutes.After stirring, 0.5g potassium peroxydisulfate is dissolved in 10ml distilled water, is added to three-necked flask In, and the N, N, N of 100 microlitres of addition, N- tetramethylethylenediamine stir 1h.Product vacuum filtration, and three times with ethanol washing, Subsequent 30 degrees Celsius are dried in vacuum overnight, and after dry, product taking-up are put into hermetic bag, inflated with nitrogen saves backup.
[embodiment 4]
The preparation of nano zero valence iron (nZVI)
(1) 4.84g Iron trichloride hexahydrate (FeCl3·6H2O) it is dissolved in (ethyl alcohol in 50mL deionized water and straight alcohol mixed solution It is 4:1 with deionized water volume ratio), it pours into there-necked flask, stirs 10min under a nitrogen atmosphere.
(2) by the NaBH of the 0.93M of 100mL4It is added dropwise in there-necked flask, simultaneously inflated with nitrogen prevents from aoxidizing for strong stirring. To ensure sufficiently to react.The color of mixed liquor becomes light yellow from rufous, eventually becomes black.Meanwhile it is mixed in there-necked flask It closes in liquid and generates more and more black particles.After being added dropwise to complete, then with normal speed stirring 20min.
(3) magnetic after the completion of stirring, is placed in bottom of bottle for magnet, product is made all to gather bottom of bottle, until complete with supernatant It separates.Product is filtered out using vacuum filtration.Product is got express developed three times to get to nZVI with dehydrated alcohol.Later by it It puts in a vacuum drying oven, temperature is kept for 60 DEG C, stores a night.
(4) after dry, case to be dried is down to room temperature, takes out product and is put into hermetic bag, inflated with nitrogen saves.
[embodiment 5]
The preparation of alta-mud loaded nano Zero-valent Iron (B-nZVI):
Step A: 4.84g Iron trichloride hexahydrate (FeCl is taken3·6H2O it) is dissolved in 50mL deionized water and straight alcohol mixed solution (volume ratio of second alcohol and water is 4:1), is added 1g bentonite, the electric stirring 10min under nitrogen filled protection environment；
Step B: by 100mL, 0.93molL-1NaBH4It is dripped in mixed liquor with the speed of 1-2 drop per second, is then existed Strong stirring under nitrogen filled protection environment.The color of mixed liquor becomes light yellow from rufous, eventually becomes black, meanwhile, three mouthfuls More and more black particles are generated in mixed liquor in bottle.NaBH4After dripping, by mixed liquor under conditions of nitrogen filled protection Persistently stir 20min, it is ensured that reaction is uniform, thoroughly.
Step C: magnet is placed in bottom of bottle, product is made all to gather bottom of bottle by magnetic after the reaction was completed, until complete with supernatant It is complete to separate, it is then filtered by vacuum, filters out product.It is got express developed three times with dehydrated alcohol to get alta-mud loaded nano Zero-valent Iron Granule electrode.It places it in vacuum oven later, is kept for 60 DEG C, store a night.
After drying, case to be dried is down to room temperature, takes out product and is put into hermetic bag, inflated with nitrogen saves.
[experimental example 1]
With the load of lignin graft bentonite prepared by embodiment 3 nano zero-valence iron composite material (BL-nZVI) and in fact Alta-mud loaded nano Zero-valent Iron (B-nZVI) prepared by the nano zero valence iron (nZVI) and embodiment 5 for applying the preparation of example 4 scans Electronic Speculum.Scanning result is as shown in Figure 1.
, it is apparent that nano zero valence iron is uniformly distributed on bentonite surface in Fig. 1 (c) and load capacity is big.Fig. 1 (a) In nano zero valence iron apparent agglomeration occurs, this certainly will will affect its effective performance, nano zero valence iron group in Fig. 1 (b) Poly- phenomenon is reduced, but its load capacity on bentonite surface is smaller, is not dispersed effectively, this must also will affect its property Energy.Nano zero valence iron nano zero valence iron (BL-nZVI) (c), nano zero valence iron are loaded by comparison lignin graft bentonite (nZVI) scanning electron microscope (SEM) photograph of the nano zero valence iron (B-nZVI) (b) of (a) and alta-mud load, it can be seen that new material of the present invention The dispersibility and stability of middle nano zero valence iron are obviously improved.
[experimental example 2]
Implement through the load of lignin graft bentonite prepared by embodiment 3 nano zero-valence iron composite material (BL-nZVI) Alta-mud loaded nano Zero-valent Iron (B-nZVI) prepared by nano zero valence iron (nZVI) and embodiment 5 prepared by example 4 carries out infrared And XRD analysis, as can be seen that Fig. 2 (c) lignin graft bentonite load nano zero valence iron is provided with simultaneously from infrared spectrum The characteristic peak of Fig. 2 (a) alta-mud loaded nano Zero-valent Iron and Fig. 2 (b) lignin, it is known that bentonite and lignin have carried out effectively Grafting；In XRD spectra, the feature of comparison diagram 2 (c) nano zero valence iron and Fig. 2 (b) alta-mud loaded nano Zero-valent Iron at 45 ° Peak, Fig. 2 (a) lignin graft bentonite load nano zero valence iron also occur the absorption peak of apparent Zero-valent Iron at 45 °, it was demonstrated that The generation of nano zero valence iron in new material, lignin graft bentonite known to comprehensive infrared and XRD spectra load nano zero valence iron Composite material is successfully prepared.
[experimental example 3]
It 25 DEG C of room temperature, under the conditions of initial sewage pH, is grafted respectively using the lignin of iron-content identical (0.2g ferro element) Alta-mud loaded nano Zero-valent Iron (BL-nZVI), nano zero valence iron (nZVI) and alta-mud loaded nano Zero-valent Iron (B-nZVI) Three kinds of materials handle paper waste (respectively taking 100mL), assist mechanical stirring (120 revs/min), at regular intervals (10 minutes) take appropriate waste water, after the filtering of 0.2 micron membrane filter, carry out COD measurement (national standard GB- using potassium dichromate method 11914-1989), and the comparison diagram for having made three kinds of material C OD removal rates has been drawn.Such as Fig. 3.
As can be seen from Figure 3 the treatment effect of Bl-nZVI will be substantially better than other two kinds of materials.

Claims (9)

1. lignin graft bentonite loads nano zero-valence iron composite material, it is characterised in that: lignin and bentonite to be grafted Nano zero valence iron is loaded, is made by following methods:
S1. bentonite and lignin are added in ferric trichloride or ferrous sulfate aqueous solution under inert gas shielding, and acutely stirred It mixes to obtain mixed liquor；
S2. successively by sodium borohydride aqueous solution, acrylamide aqueous solution and N, N'- methylene-bisacrylamide aqueous solution is added mixed It closes in liquid, initiator is added after stirring；
S3. after the reaction was completed, separate, purification is dried in vacuo to obtain composite material target product.
2. lignin graft bentonite according to claim 1 loads nano zero-valence iron composite material, it is characterised in that true It is saved backup under the composite material inert gaseous environment that sky is dried to obtain.
3. lignin graft bentonite according to claim 1 or 2 loads nano zero-valence iron composite material, feature exists In: the mass ratio of lignin, bentonite and ferro element is 1:(0.5~1.5): (0.5~1.5).
4. lignin graft bentonite according to claim 1 or 2 loads nano zero-valence iron composite material, feature exists In: the mass ratio of lignin and acrylamide is 1:(1.0~5.0).
5. lignin graft bentonite according to claim 1 or 2 loads nano zero-valence iron composite material, feature exists In: lignin and N, the mass ratio of N'- methylene-bisacrylamide are 1:(0.1~0.75).
6. lignin graft bentonite according to claim 1 or 2 loads nano zero-valence iron composite material, feature exists In: the initiator be potassium peroxydisulfate and N, N, N, N- tetramethylethylenediamine,
The mass ratio of lignin and potassium peroxydisulfate is 1:(0.1~0.75)；
Lignin and N, N, N, the mass ratio of N- tetramethylethylenediamine are 1:(0.02~0.05).
7. lignin graft bentonite according to claim 1 or 2 loads nano zero-valence iron composite material, feature exists In: reaction temperature is 25~60 DEG C.
8. lignin graft bentonite loads nano zero valence iron composite material and preparation method thereof: characterized by the following steps:
S1. bentonite and lignin are added in ferric chloride aqueous solutions under inert gas shielding, and are vigorously stirred and are mixed Liquid；
S2. successively by sodium borohydride aqueous solution, acrylamide aqueous solution and N, N'- methylene-bisacrylamide aqueous solution is added mixed It closes in liquid, initiator is added after stirring；
S3. after the reaction was completed, separate, purification is dried in vacuo to obtain composite material target product.
9. lignin graft bentonite according to claim 8 loads nano zero valence iron composite material and preparation method thereof, special Sign is: saving backup under the composite material inert gaseous environment being dried in vacuo.
CN201710240177.2A 2017-04-13 2017-04-13 Lignin graft bentonite loads nano zero valence iron composite material and preparation method Expired - Fee Related CN107081137B (en)

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CN110743552B (en) * 2019-11-07 2022-06-07 西安石油大学 Clay loaded zero-valent metal heavy oil hydrothermal cracking catalyst and its prepn
CN113769721A (en) * 2021-09-28 2021-12-10 上海大学 Preparation method and application of novel lignin hydrogel loaded nZVI material
CN114146692A (en) * 2021-12-07 2022-03-08 北华大学 Nano zero-valent iron-lignin composite material and application thereof
CN114590873A (en) * 2022-03-17 2022-06-07 山东太平洋环保股份有限公司 Three-dimensional electro-catalysis device and method for synchronously removing organic pollutants and total nitrogen

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