CN106117390A - Preparation method, adsorbent and the application of 3 D chitosan metal ring coordination compound - Google Patents
Preparation method, adsorbent and the application of 3 D chitosan metal ring coordination compound Download PDFInfo
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- CN106117390A CN106117390A CN201610482539.4A CN201610482539A CN106117390A CN 106117390 A CN106117390 A CN 106117390A CN 201610482539 A CN201610482539 A CN 201610482539A CN 106117390 A CN106117390 A CN 106117390A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- 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
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- B01J20/267—Cross-linked polymers
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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Abstract
The invention discloses preparation method, adsorbent and the application of a kind of 3 D chitosan metal ring coordination compound, preparation method includes: (1) dissolves chitosan in aqueous acetic acid, add metal sulfate, continue stirring to solution jelly, complete cross-linking reaction；(2) colloidal solution is added drop-wise in ammonia spirit, washing, dries and obtain described 3 D chitosan metal ring coordination compound.The chitosan-metal cyclic complex of the present invention, from the angle of macromolecular material, it is proposed that the material structure form of a kind of novelty, and its form is regular, compact conformation, beneficially the exploitation of material shape new ideas.Chitosan itself has the best Economic Application and is worth, and application is the most constantly widened, the application prospect of its metal ring coordination compound more industrialization；The chitosan-metal cyclic complex that the present invention prepares, material is pure, easy and simple to handle, and Financial cost is low, can be applied in engineering of water treatment as a kind of novel adsorbent.
Description
Technical field
The invention belongs to technical field of absorbent, be specifically related to the system of a kind of 3 D chitosan-metal ring coordination compound
Preparation Method, adsorbent and application.
Background technology
In recent years, increasing pollutant cause a series of water by municipal refuse discharge and industrial wastewater discharge
Contamination accident, shortage of water resources and water environment pollution will constitute safely huge, serious and potential prestige to human life
The side of body.Therefore, people increasingly pay attention to the improvement to water environment.Compared with conventional art, the skill that absorption separates as a kind of fluid
Art application in terms of water process is increasingly subject to pay attention to widely, particularly in poisonous in water body, harmful and difficult for biological degradation dirt
The removal of dye thing, absorption method has the features such as reagent dosage is few, energy consumption is low, technological process is simple and is widely applied.But,
Adsorbent, owing to having that cost is high, efficiency is low and the shortcoming such as environmental toxic, greatly limit the application of adsorption technology.Therefore,
A kind of low cost of research and development, multi-functional adsorbent efficient, eco-friendly are compeled at the tip of the brow.
Along with the development of society, the mankind be devoted to the research of material towards functionalization, become more meticulous, Composite, sublimate, intelligence
The direction of energyization is developed, and the object of study of people is concentrated mainly on resourceful natural resources.Chitin is a kind of natural many
Polysaccharide, is mainly derived from Crustacean, it is estimated that, the earth is more had by biosynthetic chitin every year
10Gt (10,000,000,000 tons), is second-biggest-in-the-world renewable natural resource.
Chitosan (chitosan) is de-acetyl chitin and a kind of biopolymer of obtaining, and its dissolubility is significantly
Be better than chitin, with chitin natural, nontoxic, good biocompatibility be prone to the advantages such as degraded, so chitosan tool
Having the best Economic Application to be worth, its application is the most constantly widened.Chitosan molecule has-OH and-NH2Side base,
Being typical Lewis basic group, from conformation, they are all equatorial bonds, and this special construction makes them to having
Some metal ions of certain ionic radius have chelation under certain pH value condition, are a kind of natural chelators, can
Stable chelate is formed as part and metal ion.Meanwhile, transition metal due to the uniqueness of its structure, formation various
Coordination compound has catalysis activity the most to some extent, have also been obtained relatively broad answering in making adsorbent research simultaneously
With.
Research for chitosan has different classification from different angles.Say from materialogy angle and generally can be divided into shell
The research of polysaccharide itself, chitosan and other materials carry out the research that is combined and the research to chitin modified material.And for
The preparation method of chitosan material is exactly mainly research of the research to chitosan solution and chitosan gel rubber etc..
From the point of view of the state this respect of the material after molding prepared by chitosan, chitosan material can be divided into zero dimension material, one
Dimension material, two-dimensional material and three-dimensional material.People have developed a series of chitosan material for a long time, but due to
Its intermolecular force is bigger, it is difficult to molding, prepares chitosan three-dimensional material and has become chitosan research circle a great problem.
Summary of the invention
The invention provides the regular three-dimensional polymer chitosan-metal ring coordination compound of a kind of environmental friendliness, form
Preparation method, the method step is simple, operates easy, low cost.
Invention also provides three-dimensional polymer chitosan-metal ring coordination compound that a kind of border is friendly, form is regular
Adsorbent.
Present invention also offers a kind of three-dimensional polymer chitosan-metal ring complex adsorption agent dirty in absorbing water body
The application of dye thing.
The preparation method of a kind of 3 D chitosan-metal ring coordination compound, comprises the steps:
(1) cross-linking reaction of sulfate radical induction: dissolve chitosan in aqueous acetic acid, add metal sulfate, continue
Continuous stirring to solution jelly, completes cross-linking reaction；
(2) self assembling process: the jelly that step (1) obtains is added drop-wise in ammonia spirit, washing, dry described in obtaining
3 D chitosan-metal ring coordination compound；
Described metal sulfate is selected from iron sulfate (Fe2(SO4)3), nickel sulfate (NiSO4·6H2O), manganese sulfate (MnSO4·
H2O), magnesium sulfate (MgSO4·7H2O), cobaltous sulfate (CoSO4·7H2O), aluminum sulfate (Al2(SO4)3·18H2O), cerous sulfate (Ce2
(SO4)3·8H2Etc. O) one or more in.As preferably, described metal sulfate selected from iron sulfate, cobaltous sulfate, aluminum sulfate,
One or more in cerous sulfate.As further preferably, described metal sulfate is iron sulfate, cerous sulfate.
As preferably, the present invention uses chitosan molecule amount be selected from molecular weight 80～120,000, deacetylation be 85～
The chitosan of 95%.
In view of the dissolubility of chitosan, as preferably, the concentration of volume percent of described aqueous acetic acid is 1～5%,
More preferably 1.5～2.5%.Select this technical scheme, it is possible to more preferably dissolve chitosan faster.
As preferably, after chitosan is dissolved in aqueous acetic acid, the concentration of chitosan is 20～50g/L, further preferably
It is 25～35g/L.So that forming the more preferable 3 D chitosan of absorption property-metal ring coordination compound.
As preferably, with mole calculating of chitosan monomer, described chitosan is 1:1～4 with the mol ratio of sulfate radical；Institute
The mol ratio stating chitosan and metal ion is 1:0.5～2.5.Or described chitosan is 1:0.3 with the mol ratio of sulfate
～2.5.
In step (1), magnetic agitation under room temperature can be used.When adding metal sulfate, the mode being slowly added dropwise can be used,
Ensure the carrying out that cross-linking reaction is stable.Response time is generally 3～5 hours.
In step (2), syringe dropping step (1) colloidal solution that obtains can be used, as preferably, the syringe needle of syringe
Internal diameter is 80～120mm, more preferably 90～110mm.The mass percent concentration of described ammonia is 20～30%, enters
One step is preferably 25～28%.
As preferably, washing process can use water and ethanol to wash successively.Described drying course is to dry in forced air drying
Case dries 1～3h for 40～60 DEG C naturally.
The preparation method of above-mentioned chitosan-metal ring coordination compound, experimental provision is simple, operates easy.Prepare
Chitosan-metal ring coordination compound, environmental friendliness, material is pure, and Financial cost is low, can as a kind of multi-functional adsorbent,
It is applied to the removal of multiple pollutant in water body.
Invention also provides a kind of 3 D chitosan-metal ring coordination compound prepared by any of the above-described method
Adsorbent.
Present invention also offers a kind of application utilizing above-mentioned adsorbent Organic Pollutants In Water.As preferably,
Described organic pollution includes Xylene Red (AR73) anionic dye, hexavalent chromium or fluorion.
As preferably, described organic pollution is Xylene Red (AR73) anionic dye；Described metal sulfate is sulphuric acid
One or more in ferrum, aluminum sulfate, cobaltous sulfate and cerous sulfate.
As preferably, described organic pollution is hexavalent chromium；Described metal sulfate is iron sulfate, aluminum sulfate, sulfur
One or more in acid cobalt and cerous sulfate.As further preferably, described metal sulfate is in iron sulfate and cerous sulfate
One or both.
As preferably, described organic pollution is fluorion；Described metal sulfate is in cerous sulfate and aluminum sulfate
Plant or multiple.
The cross-linking reaction that the present invention mentions refers to that a kind of chemistry that macromolecule molecule and cross-linking agent interact and occur is anti-
Should.In cross-linking process, the amido on chitosan difference chain protonates formation NH in the presence of glacial acetic acid3 +, as matter
Sub-donor, and after with the addition of sulfate, it is in the SO between two amino4 2-Ionic bridge beam effect is played during proton transfer,
Enhance cross-linked chitosan stability in acid condition, as shown in Figure 1.As preferably, in system, the concentration of sulfate radical takes
The total charge dosage that sulfate anion is carried controls at 0.01mol/e, the too low cross-linking effect that do not reaches of sulfate concentration, and excessive
Cross-link the free amino group that then easy consumption is too much, thus cause the minimizing of chitosan and metal-complexing, as preferably, cross-linking reaction
Time controls at about 4 hours.
Formation nature its autonomous process of assembling in ammonia indispensable of chitosan-metal ring coordination compound.As excellent
Choosing, uses 100mm internal diameter syringe needle, and the syringe of 1mL capacity dropwise instills the colloidal solution that step (1) obtains, passes through chitosan
Drop is the difference of surfaces externally and internally tension force in ammonia spirit, and drop outer surface starts to external diffusion, and drop centered is because relatively simultaneously
The gel that little surface tension is turned into a glob state irregular spins off from chitosan inner ring, makees along with the gel in ammonia
With autonomous dress, ultimately form cyclic complex hollow, compact conformation, as shown in Figure 2.
Beneficial effects of the present invention is embodied in:
(1) 3 D chitosan of the present invention-metal ring coordination compound, from the angle of macromolecular material, it is proposed that
The material structure form of a kind of novelty, its form is regular, compact conformation, beneficially the exploitation of material shape new ideas.
(2) chitosan itself has the best Economic Application value, and application is the most constantly widened, its metal complex
The application prospect of cyclic complex more industrialization；
(3) 3 D chitosan that the present invention prepares-metal ring coordination compound, material is pure, easy and simple to handle, economic one-tenth
This is low, can be applied to water body purification as a kind of novel adsorbent.
Accompanying drawing explanation
Fig. 1 is the chitosan crosslinked schematic diagram of sulfate radical induction in the present invention.
Fig. 2 is self assembling process (A) and the pictorial diagram (B, C) of metal complex cyclic complex in the present invention.
Detailed description of the invention
Embodiment 1
Dose volume mark is the glacial acetic acid solution 25mL of 2%, be slowly added to chitosan 0.75g (molecular weight is 1,000,000,
Deacetylation is 91%), continuously stirred 2h, after making chitosan fully dissolve, it is then slowly added into 0.7102g Na2SO4And continue
Stirring, cross-linking reaction 4h.After fully reacting, using 100mm internal diameter syringe needle, the syringe of 1mL capacity removes chitosan colloidal sol
Dropwise instill equipped with in the culture dish of the ammonia spirit of 25%, after cyclic complex just one-step forming, remove ammonia, use water, nothing
After water-ethanol respectively cleans 3 times, 50 DEG C of baking ovens dry 2h naturally, obtain the chitosan-metal ring coordination compound of compact conformation.
Embodiment 2
Dose volume mark is the glacial acetic acid solution 25mL of 2%, be slowly added to chitosan 0.75g (molecular weight is 1,000,000,
Deacetylation is 91%), continuously stirred 2h, after making chitosan fully dissolve, it is then slowly added into 0.6665g Fe2(SO4)3And
Continue stirring, cross-linking reaction 4h.After fully reacting, using 100mm internal diameter syringe needle, the syringe of 1mL capacity removes chitosan
Colloidal sol dropwise instills equipped with in the culture dish of the ammonia spirit of 28%, removes ammonia, use after cyclic complex just one-step forming
After water, dehydrated alcohol respectively clean 3 times, 50 DEG C of baking ovens dry 2h naturally, and the chitosan-metal ring obtaining compact conformation coordinates
Thing.
Embodiment 3
Dose volume mark is the glacial acetic acid solution 25mL of 2%, be slowly added to chitosan 0.75g (molecular weight is 1,000,000,
Deacetylation is 91%), continuously stirred 2h, after making chitosan fully dissolve, it is then slowly added into 1.3142g NiSO4·6H2O
And continue stirring, cross-linking reaction 4h.After fully reacting, using 100mm internal diameter syringe needle, the syringe of 1mL capacity is removed shell and is gathered
Sugar sol dropwise instills equipped with in the culture dish of the ammonia spirit of 27%, removes ammonia, make after cyclic complex just one-step forming
After respectively cleaning 3 times with water, dehydrated alcohol, 50 DEG C of baking ovens dry 2h naturally, and the chitosan-metal ring obtaining compact conformation coordinates
Thing.
Embodiment 4
Dose volume mark is the glacial acetic acid solution 25mL of 2%, be slowly added to chitosan 0.75g (molecular weight is 1,000,000,
Deacetylation is 91%), continuously stirred 2h, after making chitosan fully dissolve, it is then slowly added into 1.2324g MgSO4·7H2O
And continue stirring, cross-linking reaction 4h.After fully reacting, using 100mm internal diameter syringe needle, the syringe of 1mL capacity is removed shell and is gathered
Sugar sol dropwise instills equipped with in the culture dish of the ammonia spirit of 26%, removes ammonia, make after cyclic complex just one-step forming
After respectively cleaning 3 times with water, dehydrated alcohol, 50 DEG C of baking ovens dry 2h naturally, and the chitosan-metal ring obtaining compact conformation coordinates
Thing.
Embodiment 5
Dose volume mark is the glacial acetic acid solution 25mL of 2%, be slowly added to chitosan 0.75g (molecular weight is 1,000,000,
Deacetylation is 91%), continuously stirred 2h, after making chitosan fully dissolve, it is then slowly added into 1.1107g Al2(SO4)3·
18H2O also continues stirring, cross-linking reaction 4h.After fully reacting, using 100mm internal diameter syringe needle, the syringe of 1mL capacity is removed
Chitosan colloidal sol dropwise instills equipped with in the culture dish of the ammonia spirit of 25%, falls deammoniation after cyclic complex just one-step forming
Water, after using water, dehydrated alcohol respectively to clean 3 times, 50 DEG C of baking ovens dry 2h naturally, obtain the chitosan-becket of compact conformation
Shape coordination compound.
Embodiment 6
Dose volume mark is the glacial acetic acid solution 25mL of 2%, be slowly added to chitosan 0.75g (molecular weight is 1,000,000,
Deacetylation is 91%), continuously stirred 2h, after making chitosan fully dissolve, it is then slowly added into 0.8451g MnSO4·H2O is also
Continue stirring, cross-linking reaction 4h.After fully reacting, using 100mm internal diameter syringe needle, the syringe of 1mL capacity removes chitosan
Colloidal sol dropwise instills equipped with in the culture dish of the ammonia spirit of 28%, removes ammonia, use after cyclic complex just one-step forming
After water, dehydrated alcohol respectively clean 3 times, 50 DEG C of baking ovens dry 2h naturally, and the chitosan-metal ring obtaining compact conformation coordinates
Thing.
Embodiment 7
Dose volume mark is the glacial acetic acid solution 25mL of 2%, be slowly added to chitosan 0.75g (molecular weight is 1,000,000,
Deacetylation is 91%), continuously stirred 2h, after making chitosan fully dissolve, it is then slowly added into 1.4055g CoSO4·7H2O
And continue stirring, cross-linking reaction 4h.After fully reacting, using 100mm internal diameter syringe needle, the syringe of 1mL capacity is removed shell and is gathered
Sugar sol dropwise instills equipped with in the culture dish of the ammonia spirit of 25%, removes ammonia, make after cyclic complex just one-step forming
After respectively cleaning 3 times with water, dehydrated alcohol, 50 DEG C of baking ovens dry 2h naturally, and the chitosan-metal ring obtaining compact conformation coordinates
Thing.
Embodiment 8
Dose volume mark is the glacial acetic acid solution 25mL of 2%, be slowly added to chitosan 0.75g (molecular weight is 1,000,000,
Deacetylation is 91%), continuously stirred 2h, after making chitosan fully dissolve, it is then slowly added into 1.1876g Ce2(SO4)3·
8H2O also continues stirring, cross-linking reaction 4h.After fully reacting, using 100mm internal diameter syringe needle, the syringe of 1mL capacity is removed
Chitosan colloidal sol dropwise instills equipped with in the culture dish of the ammonia spirit of 28%, falls deammoniation after cyclic complex just one-step forming
Water, after using water, dehydrated alcohol respectively to clean 3 times, 50 DEG C of baking ovens dry 2h naturally, obtain the chitosan-becket of compact conformation
Shape coordination compound.
Absorption test case 1
Embodiment 1～8 is removed Xylene Red (AR73) anionic dye simultaneously and is detected by applicant, specific as follows:
The ring-type chitosan complex 0.02g of what respectively prepared by Example 1-8 chelated different metal is separately added into
10mL concentration is in the AR73 solution of 50mg/L, shaken at room temperature 1 hour, takes supernatant and crosses film (0.2um) at uv-spectrophotometric
Analyzing at instrument 509nm and measure, acquired results is shown in Table 1.
Table 1
As shown in Table 1, the ring-type chitosan material utilizing embodiment 1 to prepare is with Na2SO4Make cross-linking agent, due to sodium
Ion is not involved in chelatropic reaction, and the adsorption effect of embodiment 1 is owing to the adsorption of chitosan itself.Embodiment 2,5,7,8
Adsorption effect be all higher than 91.0%, this explanation has chelated Fe3+、Al3+、Co2+And Ce3+Isoionic chitosan cyclic complex
The chitosan molecule removal efficiency to AR73 can be significantly improved.
Absorption test case 2
Embodiment 1,2,5,7,8 is removed hexavalent chromium (Cr (VI)) simultaneously and is detected by applicant, specific as follows:
What Example 1,2,5,7,8 prepared respectively has chelated the ring-type chitosan complex 0.02g of different metal
It is separately added in Cr (VI) solution that 10mL concentration is 50mg/L, shaken at room temperature 1 hour, takes supernatant and cross film (0.2um), use
Diphenyl carbazide spectrophotometry measures Cr (VI) concentration in solution, and acquired results is shown in Table 2.
Table 2
As shown in Table 2, obtain composite prepared by the embodiment 1 of non-chelated mineral the clearance of Cr (VI) is only had
50.8%.And cross-link and chelated Fe3+、Ce3+After ion, the chitosan cyclic complex that embodiment prepares is to Cr's (VI)
Clearance all can reach more than 90%, and this is owing to Fe on chitosan (III) or the collaborative chelation of Ce (III), it will be apparent that
Improve the chitosan removal efficiency to Cr (VI).
Absorption test case 3
Embodiment 1,2,5,8 is removed Natural zeolite (F by applicant simultaneously-) detected, specific as follows:
The ring-type chitosan complex 0.02g of what Example 1,2,5,8 prepared respectively chelated different metal divides
Jia Ru 10mL concentration be not the F of 10mg/L-In solution, shaken at room temperature 1 hour, take supernatant and cross film (0.2um), use fluorion
Select F in determination of electrode solution-Concentration, acquired results is shown in Table 3.
Table 3
As shown in Table 3, composite is obtained to F prepared by the embodiment 1 of non-chelated mineral-Clearance only have 2.0%,
This explanation chitosan itself does not possess absorption F-Ability.And cross-link and chelated Fe3+、Al3+、Ce3+After, prepared by embodiment 2,5,8
The chitosan obtained-metal ring coordination compound is to F-Clearance significantly improve, wherein chitosan-Ce (III) cyclic complex
To F-Clearance can be up to more than 90%, during this lives for us, the technology of Fluoride Removal of drinking water provides strong hands
Section.
Claims (10)
1. the preparation method of 3 D chitosan-metal ring coordination compound, it is characterised in that comprise the steps:
(1) dissolve chitosan in aqueous acetic acid, add metal sulfate, continue stirring to solution jelly, complete to hand over
Connection reaction；
(2) jelly that step (1) obtains is added drop-wise in ammonia spirit, washing, dries and obtain described 3 D chitosan-gold
Belong to cyclic complex.
The preparation method of 3 D chitosan the most according to claim 1-metal ring coordination compound, it is characterised in that described
Metal sulfate one in iron sulfate, nickel sulfate, cobaltous sulfate, magnesium sulfate, sodium sulfate, manganese sulfate, aluminum sulfate, cerous sulfate
Or it is multiple.
The preparation method of 3 D chitosan the most according to claim 1-metal ring coordination compound, it is characterised in that described
The concentration of volume percent of aqueous acetic acid is 1～5%；After chitosan is dissolved in aqueous acetic acid, the concentration of chitosan is 20
～50g/L.
The preparation method of 3 D chitosan the most according to claim 1-metal ring coordination compound, it is characterised in that with shell
Mole calculating of polysaccharide monomer, described chitosan is 1:1～4 with the mol ratio of sulfate radical；Described chitosan and metal ion
Mol ratio is 1:0.5～2.5.
The preparation method of 3 D chitosan the most according to claim 1-metal ring coordination compound, it is characterised in that step
(2) in, using the colloidal solution that syringe dropping step (1) obtains, the syringe needle internal diameter of syringe is 80～120mm, described
The mass percent concentration of ammonia is 20～30%.
6. 3 D chitosan-metal ring complex adsorption agent, it is characterised in that by right arbitrary in claim 1-5
Preparation method described in requirement prepares.
7. the application of organic pollution in a metal complex chitosan absorbent adsorbed water body, it is characterised in that described metal
Complexation chitosan absorbent is the 3 D chitosan described in claim 6-metal ring complex adsorption agent, described organic contamination
Thing includes Xylene Red anionic dye, hexavalent chromium or fluorion.
The application of organic pollution in metal complex chitosan absorbent adsorbed water body the most according to claim 7, it is special
Levying and be, described organic pollution is Xylene Red anionic dye；Described metal sulfate is iron sulfate, aluminum sulfate, cobaltous sulfate
With one or more in cerous sulfate.
The application of organic pollution in metal complex chitosan absorbent adsorbed water body the most according to claim 7, it is special
Levying and be, described organic pollution is hexavalent chromium；Described metal sulfate is the one in iron sulfate and cerous sulfate or many
Kind.
The application of organic pollution in metal complex chitosan absorbent adsorbed water body the most according to claim 7, it is special
Levying and be, described organic pollution is fluorion；Described metal sulfate is one or more in cerous sulfate and aluminum sulfate.
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| CN106904709A (en) * | 2017-03-27 | 2017-06-30 | 山东钢铁集团日照有限公司 | A kind of method for preparing hollow ball flocculant |
| CN106830251A (en) * | 2017-04-12 | 2017-06-13 | 国网山东省电力公司电力科学研究院 | Recombination chitosan flocculant and preparation method and application for processing desulfurization wastewater |
| CN107282023A (en) * | 2017-08-25 | 2017-10-24 | 益阳医学高等专科学校 | A kind of chemical waste fluid processing nano adsorber and preparation method thereof |
| CN107282023B (en) * | 2017-08-25 | 2020-05-19 | 益阳医学高等专科学校 | Nano adsorbent for chemical waste liquid treatment and preparation method thereof |
| CN107413318A (en) * | 2017-09-01 | 2017-12-01 | 陈京帅 | A kind of industrial wastes processing efficient nano adsorbent and preparation method thereof |
| CN107413318B (en) * | 2017-09-01 | 2020-09-11 | 浙江致远环境科技有限公司 | Efficient nano adsorbent for industrial waste liquid treatment and preparation method thereof |
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