CN108530935A - A kind of polyaniline composite functional material, preparation method and application - Google Patents
A kind of polyaniline composite functional material, preparation method and application Download PDFInfo
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- CN108530935A CN108530935A CN201810315187.2A CN201810315187A CN108530935A CN 108530935 A CN108530935 A CN 108530935A CN 201810315187 A CN201810315187 A CN 201810315187A CN 108530935 A CN108530935 A CN 108530935A
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- aniline monomer
- polyaniline
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 105
- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000011651 chromium Substances 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 235000019441 ethanol Nutrition 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract 2
- 238000001179 sorption measurement Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229940008099 dimethicone Drugs 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 23
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 6
- 238000001784 detoxification Methods 0.000 abstract description 4
- 239000011858 nanopowder Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 235000012721 chromium Nutrition 0.000 description 24
- 239000003463 adsorbent Substances 0.000 description 20
- 229960000892 attapulgite Drugs 0.000 description 12
- 229910052625 palygorskite Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 235000011167 hydrochloric acid Nutrition 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 239000004927 clay Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- 206010000087 Abdominal pain upper Diseases 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- -1 amino imino functional group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 208000018556 stomach disease Diseases 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of polyaniline composite functional material, preparation method and applications, belong to field of waste water treatment.The preparation method of the material includes the following steps：1) purification of aniline monomer；2) aniline monomer disperses：It pipettes in the aniline monomer disperse water after purification, is stirred at room temperature, obtains aniline monomer dispersion liquid；3) it mixes：Resin is weighed, ethyl alcohol impregnates, after washing, is placed in the aniline monomer dispersion liquid in step 2), stirring, obtains mixed liquor；4) preparation of oxidant；5) oxidant is added drop-wise in the mixed liquor in step 3), after being added dropwise, stands stirring, product filtering, alcohol wash, are washed to neutral, drying.The composite functional material can not only adsorb the Cr VI in waste water, and further can convert hexavalent chrome reduction to trivalent chromium, realize that the detoxification treatment of chromate waste water and resource utilization utilize；The defect that polyaniline nano powder is not easy to water body application is overcome, large-scale production and application are convenient for.
Description
Technical field
The invention belongs to water pollution process field, it is related to the reduction of Cr VI and Adsorption in water, and in particular to a kind of
Polyaniline composite functional material, preparation method and application.
Background technology
Chromium and compound is widely used in modern industry, and the industry such as ink, dyestuff, plating and chromium legal system leather is not all from
Chromium compound is opened, can contain the different chromium of quantity in the waste water of these industrial discharges.Chromium is in water with sexavalence (Cr2O7 2-, CrO4 2-
Trivalent (CrO2-,Cr3+) ionic forms exist, mainly exist in the form of sexavalence in industrial wastewater.People is drinking by the water of pollution of chromium
After can cause stomach pain and the diseases such as functions of intestines and stomach disorder even carcinogenic and aberration inducing.In addition chromium is to water body fish, microorganism
And the growth of certain crops also has inhibiting effect, to which the utilization of water and the self-purification function of water body can be influenced.State Ministry of Environmental Protection
Goalkeeper's chromate waste water is classified as a class of pollutant, the stringent direct emission for controlling chromate waste water.Therefore, for the processing of Cr VI one
It is directly the research hotspot in home and abroad environment field.
Currently, including industrially mainly ion-exchange, electrochemical process, reverse osmosis to the treating method of chromyl waste water
It the advantages that saturating the methods of method and absorption method, wherein absorption method is due to easy to operate, safety, simple equipment, is most widely used.On
It states processing method and there is certain limitation, such as removal amount is low, the serious serious problems of secondary pollution.At present for, research compared with
More adsorbents mainly has carbon absorbent and organic polymer etc., but most of adsorbents are still in laboratory research rank
Section, therefore the adsorbent for developing good, convenient for production application the Adsorption for chromium of adsorption effect is that processing is useless containing chromium
One important direction of water.
Polyaniline contains a large amount of amino imino functional group as a kind of novel conducting polymer in molecule,
They have good complexing to metal ion, while these amino iminos also have reproducibility, can be with some oxygen
Change the high metal ion of reduction potential and redox reaction occurs, simultaneously because it is with good solvent resistance, so can
To be widely used in various complex environment conditions.Existing research shows that polyaniline for Cr VI have it is relatively high
Adsorption capacity, be preferably to remove chromium adsorbent, while the imino group functional group on polyaniline can also effectively restore sexavalence
Chromium is the lower trivalent chromium of toxicity.In order to improve adsorption capacity of the polyaniline to chromium, various carriers such as clay, nanofiber, magnetic
The carrier that property nano-particle etc. is used for polyaniline prepares polyaniline composite material, but this kind of composite material is still with dispersibility
Dispersion, be still detrimental to application of the polyaniline in practical water body.
In the prior art, the preparation method of polyaniline is generally：Aniline monomer is disperseed in an acidic solution, keeps low temperature
It is slowly added to the oxidant configured.It is existing poly- in the prior art in order to preferably play the application of polyaniline in the environment
The research of aniline associated materials, such as Chinese Patent Application No. CN201110205090.4, publication date is the Shen of 2012.02.15
Please case disclose a kind of method for removing Cr VI in water removal using polyaniline-modified attapulgite, the method for this application exists first
Under conditions of ice-water bath, aniline and p-phenylenediamine is dissolved in the hydrochloric acid solution of a concentration of 1mol/L, adds attapulgite, stirred
It mixes uniformly；Then, it dissolves ammonium persulfate into the hydrochloric acid solution of other a concentration of 1mol/L；Finally, first two steps are obtained
It after solution mixing carries out polymerisation, is stored at room temperature, filters later, wash, it is dry, it is multiple to obtain polyaniline-modified attapulgite
Particle is closed, is 1 in mass ratio by the water of polyaniline-modified attapulgite clay compounded particle obtained and Cr VI to be removed：800
~5000 mixing, can effectively remove the Cr VI in the waste water that Cr VI initial concentration is 2.5~35mg/L, and the present invention overcomes
The disadvantage that adsorbent adsorption capacity is small, the rate of adsorption is low and adsorption efficiency is poor existing for existing adsorption method, effectively controls
Cr VI is to the pollution and harm caused by water body.However there is also following defects for the method for this application：1) polyaniline-modified
Attapulgite clay compounded particle be still to be not easy to put into extensive actual use with powder application；2) polyaniline-modified
Attapulgite clay compounded particle need to be improved to the adsorption capacity of Cr VI in water body；3) this application is not studied polyaniline and is changed
Reducing power of the attapulgite clay compounded particle of property to Cr VI.
Chinese Patent Application No. CN201710026980.6, publication date are that the application case of 2017.10.13 discloses one kind
The reduction and removal of the preparation method and applications of novel porous conductive polyaniline material Cr (VI) in waste water, using carefully
The feature of bacterium thalline easy dehydration when having certain shape but drying, is given birth to polyaniline using chemical oxidation method in aqueous solution
It grows behind microorganism surface, it is dry under the conditions of 80 DEG C so that microorganism dehydration ruptures to form hole, is prepared porous
Property polyaniline material.The template only discharges water outlet and comes, and non-secondary pollution generates, and is a kind of green template.Use bacterium for template
For the material conductivity than 10S/cm is reached, which is reduced to pH=4.5, can be achieved at the same time to Cr in waste water (VI)
Reduction and reduction after Cr (III) absorption.However there is also following defects for the method for this application：1) porous, electrically conductive polyphenyl
Amine is still to exist with the dusty material of dispersibility, is unfavorable for the application of practical water body；2) the preparation side of porous, electrically conductive polyaniline
Method difference is using template, and template is microorganism.
Defect based on the prior art, there is an urgent need for invent it is a kind of it is good to Cr VI absorption property, gather conducive to large-scale application
Phenyl composite functional material.
Invention content
1. to solve the problems, such as
In order to overcome polyaniline nano powder to be not easy to water body application and polyaniline related compound material in water body six
The absorption property of valence chromium defect to be improved, the present invention is intended to provide a kind of large specific surface area, being adsorbed to Cr VI in water body
Performance is good, is conducive to large-scale application, while can realize the polyphenyl amino that the detoxification treatment of chromate waste water and resource utilization utilize
Composite functional material.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows：
The present invention provides a kind of polyaniline composite functional material, the polyaniline composite functional material is by aniline list
Body be distributed to macroporous absorbent resin surface and endoporus in occur oxidative polymerization be made.
As further improvement of the present invention, the specific surface area of the polyaniline composite functional material is
652.6m2/ g, average pore size 10.23nm.
As further improvement of the present invention, the preparation method of the polyaniline composite functional material, feature
It is：Include the following steps：
1) purification of aniline monomer：Using aniline monomer using dimethicone as oil bath reagent, collection distillates component；
2) aniline monomer disperses：Removing step 1) in aniline monomer disperse water that treated, it is stirred at room temperature, obtains aniline list
Dispersion liquid；
3) resin pre-processes：Resin is weighed, ethyl alcohol impregnates, after washing, be placed in the aniline monomer dispersion liquid in step 2),
Stirring, obtains mixed liquor；
4) preparation of oxidant：Oxidant is weighed to be dissolved into hydrochloric acid solution；
5) oxidant is added drop-wise in the mixed liquor in step 3), after being added dropwise, stands stirring, product filters, alcohol is washed,
It is washed to neutral, dry.
As further improvement of the present invention, the mass ratio of the resin and aniline monomer is (1~6)：1.
As further improvement of the present invention, the macroporous absorbent resin is XAD-4.
As further improvement of the present invention, the oxidant is ammonium persulfate.
As further improvement of the present invention, mixing time is 6~12h in the step 3), and temperature is room temperature.
As further improvement of the present invention, the present invention provides a kind of methods of Cr VI in removal water body, use
Cr VI in the polyaniline composite functional material Adsorption water body.
As further improvement of the present invention, a concentration of 5~10mg/L of Cr VI, the pH value of water body in the water body
It is 6~8.
As further improvement of the present invention, the method further includes De contamination step, will be inhaled using acid in the step
Attached hexavalent chrome reduction is trivalent chromium.
3. advantageous effect
Compared with the prior art, beneficial effects of the present invention are：
(1) polyaniline composite functional material of the invention, using macroporous absorbent resin as carrier, in its endoporus and appearance
Face carries out the oxidation polymerization of aniline, due to the XAD-4 suction-operateds excellent to aniline so that divides equally with outer surface inside resin balls
Cloth polyaniline, is advantageous to fixation of the polyaniline in resin surfaces externally and internally；It is applied to go in water removal as adsorbent
Chromium, carry out that higher adsorbance has been calculated with the polyaniline of unit mass.Polyaniline adsorbent list prepared by the present invention
For the adsorbance of the polyaniline of position quality up to 130.55mg/g, manufactured polyaniline composite functional material may be directly applied to reality
Border waste water has a good application prospect in water pollution and reparation field.
(2) polyaniline composite functional material of the invention, adsorption specific surface area are up to 652.6m2/ g, average pore size
In 10.23nm, and the specific surface area of the polyaniline powder prepared in the prior art is only 20~50m2/ g, therefore resin and benzene
The polyaniline composite functional material that amine is formed after combining has the specific surface area of bigger, inherently improves its adsorptivity
Can, it is conducive to promote.
(3) polyaniline composite functional material of the invention has due to adsorbing the substrate effect of resin using to aniline
The macroporous absorbent resin of good adsorbent performance carries out the oxidation polymerization of aniline as carrier, on its surface, is improving polyaniline ratio
While surface area, make it easy to that there is potential application prospect using in terms of the removal for detaching Cr VI.It is apparent to improve
Polyaniline powder state is convenient for the application of actual waste water system, is effectively overcome poly- so that it can for filling adsorption column
Aniline is unfavorable for the defect of actual waste water application, has good actual application value.
(4) application of polyaniline composite functional material of the invention can use acid desorption with reality after adsorption saturation
The desorption of existing Cr VI and reduction, the same of the trivalent chromium of formation are adsorbed by polyaniline composite functional material, to form one
The control of body, and the trivalent chromium that Cr VI is desorbed and is generated after restoring in the prior art is present in water body, needs further
Removal, complex for operation step, application process of the invention can simplify operating procedure, to realize the detoxification treatment of chromate waste water
And resource utilization utilizes.
(5) polyaniline composite functional material of the invention, in neutral conditions absorption of the unit polyaniline to Cr VI
Amount is up to 231mg/g, and the also commercial weight of unit polyaniline is up to 661mg/g under acid condition.This is mainly due to polyanilines big
Inside the duct of macroporous adsorbent resin, since the adsorption site that nano-space effect is shown increases, adsorption capacity and also
Proper energy power significantly increases.
(6) preparation method of polyaniline composite functional material of the invention, operating procedure is simple, first will be after purification
Aniline monomer is dispersed in water body, then is mixed with resin, so that aniline monomer is preferably distributed and is entrenched in resin endoporus and outer
Using the effect of oxidant in turn oxidative polymerization occurs for surface, and PANI@XAD-4 are made, and final material obtained combines
Performance of both polyaniline and resin is excellent to the adsorption rate of Cr VI in water body.
(7) preparation method of polyaniline composite functional material of the invention, choose has preferably absorption to aniline monomer
The macroreticular resin XAD of effect makes aniline monomer be more advantageous to resin endoporus and outer surface polymerization, further polyaniline is made to answer
It closes functional material and generates superior absorption property.
Specific implementation mode
Description of the drawings
Fig. 1 is the section microscope contrast schematic diagram of XAD-4 and PANI@XAD-4；
Fig. 2 is the SEM schematic diagrames of PANI@XAD-4；
Fig. 3 is the adsorption isotherm schematic diagram of PANI@XAD-4 and PANI when hexavalent chromium concentration is 10~200ppm.
Specific implementation mode
The present invention is further described below with reference to specific embodiment.
Embodiment 1
The preparation method of polyaniline composite functional material includes the following steps in the present embodiment：
1) purification of aniline monomer：Aniline monomer is placed in 500mL boiling flasks, rotary evaporator is packed into, utilizes two
Methyl-silicone oil is to slowly warm up to 350 DEG C, collection distillates component as oil bath reagent；
2) aniline monomer disperses：It pipettes the aniline monomer after purification to be distributed in 90mL water and be placed in three-necked flask, room temperature
2h is stirred, aniline dispersion liquid is obtained；
3) resin pre-processes：5g resins are weighed, are impregnated through ethyl alcohol, after washing, three mouthfuls of merging dispersion liquid containing aniline monomer
In flask, 6h is stirred at room temperature, obtains mixed liquor, the mass ratio of resin and aniline monomer is 1 in the mixed liquor：1；
4) preparation of oxidant：12.25g oxidant ammonium persulfates are weighed, are dissolved into 100mL hydrochloric acid solutions；
5) 9.5mL concentrated hydrochloric acids are instilled into the three-necked flask in step 3), and slowly oxidant is added drop-wise in three-necked flask,
Cross in title temperature control 5 hereinafter, being added dropwise after, stand stirring 6h, product filters with 200 mesh nonwoven gauzes, washed through alcohol, water
It is washed till neutrality, 50 DEG C of vacuum drying are made the polyaniline composite functional material, are named as PANI@XAD-4.
The content of polyaniline is calculated with the weightening of resin after preparation, the polyphenyl amine content that obtains unit compound adsorbent is
5.28%.It is confirmed by micropore specific area adsorption-desorption instrument, the ratio of the polyaniline composite functional material prepared in the present embodiment
Surface area is 652.6m2/ g, average pore size 10.23nm.
Wherein, Fig. 1 is the section microscope contrast schematic diagram of XAD-4 and PANI@XAD-4；Wherein, figure a indicates XAD-4's
Section microscope schematic diagram, figure b indicate the section microscope schematic diagram of ANI@XAD-4.As shown in Figure 1, PANI is in XAD-4
Portion is formed.
Fig. 2 is the SEM schematic diagrames of PANI@XAD-4, and as shown in Figure 2, PANI is formed in the outer surfaces XAD-4.
Therefore, by above-mentioned confirmation collection of illustrative plates it is found that the PANI@XAD-4 composite materials formed make inside XAD-4 resin balls and
Outer surface is dispersed with polyaniline, is advantageous to fixation of the polyaniline in resin surfaces externally and internally；Due to nano-space effect exhibition
The adsorption site revealed increases, therefore its adsorption capacity and reducing power significantly increase.
Using the PANI@XAD-4 in the present embodiment of preparation as adsorbent, the Cr VI that initial concentration is 10mg/L is handled
Simulated wastewater, pH=6.0, steps are as follows for adsorption test：
50mL chromate waste waters are added to 100mL according in plug conical flask, adsorbent 50mg (PANI@XAD-4), absorption is added
Equilibration time is 50min, adsorption capacity 141mg/gPANI, eliminating rate of absorption 75%；The removal rate of Cr VI refers to being inhaled
The concentration of attached Cr VI and the ratio of initial concentration.
, as adsorbent, to handle the sexavalence that initial concentration is 10mg/L using the polyaniline powder prepared in the prior art
Chromium simulated wastewater, pH=6.0, steps are as follows for adsorption test：
50mL chromate waste waters are added to 100mL according in plug conical flask, adsorbent 2.5mgPANI are added, break time takes
Sample, time of equilibrium adsorption 50min, adsorption capacity 72mg/gPANI, removal rate 36%；The removal rate of Cr VI refer to by
The concentration of the Cr VI of absorption and the ratio of initial concentration.Wherein, what PANI the and 50mg PANI@XAD-4 of 2.5mg contained is poly-
The amount of aniline is consistent.
Meanwhile to existing literature《A method of removing Cr VI in water removal using polyaniline-modified attapulgite》Middle use
Polyaniline-modified attapulgite clay compounded particle carry out the adsorpting data of Cr VI in water and summarize.
Table 1 is the statistical form for adsorbing contrast test.
Table 1 adsorbs contrast test statistical form
As shown in Table 1, existing literature《A method of removing Cr VI in water removal using polyaniline-modified attapulgite》In,
It uses polyaniline-modified attapulgite clay compounded particle to carry out in water in the absorption of Cr VI, adsorption capacity when adsorption equilibrium
Smaller and polyaniline-modified attapulgite clay compounded particle is still with powder application, and be not easy to input actually makes on a large scale
With；And specific surface of the PANI@XAD-4 materials that resin material XAD-4 and PANI is compounded to form due to substantially improving PANI
The performances such as product, aperture, therefore adsorption capacity and eliminating rate of absorption increase significantly.
Embodiment 2
The preparation method of polyaniline composite functional material includes the following steps in the present embodiment：
1) aniline monomer disperses：The aniline monomer after purification as described in Example 1 is pipetted to be distributed in 90mL water and be placed in three
In mouth flask, 2h is stirred at room temperature, obtains aniline dispersion liquid；
2) resin pre-processes：3g resins are weighed, are impregnated through ethyl alcohol, after washing, are placed in three containing aniline monomer dispersion liquid
In mouth flask, 10h is stirred at room temperature, obtains mixed liquor, the mass ratio of resin and aniline monomer is 6 in the mixed liquor：1；
3) preparation of oxidant：7.35g oxidant ammonium persulfates are weighed, are dissolved into 100mL hydrochloric acid solutions；
4) 9.5mL concentrated hydrochloric acids are instilled to the three-necked flask in step 3), slowly oxidant is added drop-wise in three-necked flask, mistake
In title temperature control 5 DEG C hereinafter, being added dropwise after, stand stirring 6h, product filters with 200 mesh nonwoven gauzes, washed through alcohol, water
It is washed till neutrality, 50 DEG C of vacuum drying are made the polyaniline composite functional material, are named as PANI@XAD-4.
The content of polyaniline is calculated with the weightening of resin after preparation, the polyphenyl amine content that obtains unit compound adsorbent is
4.68%.Using the polyaniline resin of preparation as adsorbent, the Cr VI simulated wastewater that processing initial concentration is 8mg/L, pH=
7.0。
50mL chromate waste waters are added to 100mL according in plug conical flask, adsorbent 50mg is added, constant temperature oscillation adsorbs,
Disconnected time sampling, time of equilibrium adsorption 30min, removal rate 50%.The removal rate of Cr VI refers to the Cr VI adsorbed
Concentration and initial concentration ratio.
Embodiment 3
The preparation method of polyaniline composite functional material includes the following steps in the present embodiment：
1) aniline monomer disperses：The aniline monomer after purification as described in Example 1 is pipetted to be distributed in 90mL water and be placed in three
In mouth flask, 2h is stirred at room temperature, obtains aniline monomer dispersion liquid；
2) resin pre-processes：3g resins are weighed, are impregnated through ethyl alcohol, after washing, are placed in three containing aniline monomer dispersion liquid
In mouth flask, 12h is stirred at room temperature, obtains mixed liquor, the mass ratio of resin and aniline monomer is 3 in the mixed liquor：1；
3) configuration of oxidant weighs 7.35g oxidant ammonium persulfates, is dissolved into 100mL hydrochloric acid solutions；
4) 9.5mL concentrated hydrochloric acids are instilled to the three-necked flask in step 3), slowly oxidant is added drop-wise in three-necked flask, mistake
In title temperature control 5 DEG C hereinafter, being added dropwise after, stand stirring 6h, product filters with 200 mesh nonwoven gauzes, washed through alcohol, water
It is washed till neutrality, 50 DEG C of vacuum drying are made the polyaniline composite functional material, are named as PANI@XAD-4.
Embodiment 4
The present embodiment is the reality that the adsorption Removal of Cr VI in water body is carried out using polyaniline composite functional material
Apply example.
It is the preparation of polyaniline composite functional material first, specific preparation process is consistent with embodiment 1.
Using the polyaniline composite functional material of preparation as adsorbent, the Cr VI mould that initial concentration is 10mg/L is handled
Quasi- waste water, pH are adjusted to 1.0 ± 0.2.50mL chromate waste waters are added to 100mL according in plug conical flask, adsorbent 50mg is added, it is permanent
Temperature oscillation absorption, break time sampling, time of equilibrium adsorption 20min, Cr VI are reduced to trivalent chromium, and reduction rate is
96.5%, the reduction rate refers to the ratio of measured trivalent chromium concentration and initial hexavalent chromium concentration.
Embodiment 5
The present embodiment is the reality that the adsorption Removal of Cr VI in water body is carried out using polyaniline composite functional material
Apply example.
It is the preparation of polyaniline composite functional material first, specific preparation process is consistent with embodiment 1.
Using the polyaniline composite functional material of preparation as adsorbent, fixed bed volume is 5mL, flow velocity 3BV.h-1,
Cr VI influent concentration is 5mg/L, initial soln pH=8, carries out the column adsorption experiment of Cr VI.
Desorption reduction carries out it using the hydrochloric acid of a concentration of 1mol/L after adsorption saturation, desorption flow velocity is 0.125mL/
min.The total adsorbance of integral and calculating is 4.38mg, and the Cr VI being reduced in desorption liquid is 4.07mg, and desorption reduction efficiency is
92.9%.
Fig. 3 is the adsorption isotherm of PANI@XAD-4 and PANI when hexavalent chromium concentration is 10~200ppm.In figure, left seat
Mark indicates that the adsorbance of Cr VI when balance, right coordinate are the concentration of the trivalent chromium generated in solution.As shown in Figure 3：1)PANI@
XAD-4 and PANI distinguishes 231.2mg/g and 58.6mg/g to Cr VI maximum reducing power；2) after PANI@XAD-4 processing
Solution in can't detect trivalent chromium completely, and pass through PANI treated in solution that there are trivalent chromiums.
Therefore, PANI@XAD-4 have stronger reducing power for Cr VI, and the trivalent chromium to being formed after processing is not
It need to be further processed, can realize that the detoxification treatment of chromate waste water and resource utilization utilize.
Schematically the invention and embodiments thereof are described above, description is not limiting, attached drawing
Shown in also be the invention one of embodiment, actual structure is not limited to this.So if this field
Those of ordinary skill enlightened by it, in the case where not departing from this creation objective, without creatively designing and the technology
The similar frame mode of scheme and embodiment, should all belong to the protection domain of this patent.
Claims (10)
1. a kind of polyaniline composite functional material, it is characterised in that：The polyaniline composite functional material is by aniline monomer
Be distributed to macroporous absorbent resin surface and endoporus in occur oxidative polymerization be made.
2. polyaniline composite functional material according to claim 1, it is characterised in that：The compound work(of the polyaniline
The specific surface area of energy material is 652.6m2/ g, average pore size 10.23nm.
3. the preparation method of polyaniline composite functional material as claimed in claim 1 or 2, it is characterised in that：Including following step
Suddenly：
1) purification of aniline monomer：Using aniline monomer using dimethicone as oil bath reagent, collection distillates component；
2) aniline monomer disperses：Removing step 1) in aniline monomer disperse water that treated, it is stirred at room temperature, obtain aniline monomer point
Dispersion liquid；
3) resin pre-processes：Resin is weighed, ethyl alcohol is impregnated, after washing, in the aniline monomer dispersion liquid being placed in step 2), stirred
It mixes, obtains mixed liquor；
4) preparation of oxidant：Oxidant is weighed to be dissolved into hydrochloric acid solution；
5) oxidant is added drop-wise in the mixed liquor in step 3), after being added dropwise, stands stirring, product filtering, alcohol are washed, washed
To neutral, drying.
4. the preparation method of polyaniline composite functional material according to claim 3, it is characterised in that：The resin and
The mass ratio of aniline monomer is (1~6)：1.
5. the preparation method of polyaniline composite functional material according to claim 1 or 2, it is characterised in that：Described
Macroporous absorbent resin is XAD-4.
6. the preparation method of polyaniline composite functional material according to claim 4, it is characterised in that：The oxidant
For ammonium persulfate.
7. the preparation method of the polyaniline composite functional material according to claim 4 or 6, it is characterised in that：The step
It is rapid 3) in mixing time be 6~12h, temperature is room temperature.
8. a kind of method of Cr VI in removal water body, it is characterised in that：Using the compound work(of polyaniline described in claim 1
Cr VI in energy material Adsorption water body.
9. the method for Cr VI in removal water body according to claim 8, it is characterised in that：Cr VI in the water body
The pH value of a concentration of 5~10mg/L, water body are 6~8.
10. the method for Cr VI in removal water body according to claim 8, it is characterised in that：The method further includes taking off
Adsorption step uses in the step acid by the hexavalent chrome reduction after absorption for trivalent chromium.
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| CN112387257A (en) * | 2020-11-05 | 2021-02-23 | 西安工程大学 | Preparation method of high-molecular polyaniline porous filler water treatment adsorbent |
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| CN112387257A (en) * | 2020-11-05 | 2021-02-23 | 西安工程大学 | Preparation method of high-molecular polyaniline porous filler water treatment adsorbent |
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