CN107694529A - A kind of preparation method of heavy metal ion and organic dyestuff Adsorption type composite aquogel - Google Patents
A kind of preparation method of heavy metal ion and organic dyestuff Adsorption type composite aquogel Download PDFInfo
- Publication number
- CN107694529A CN107694529A CN201711041132.9A CN201711041132A CN107694529A CN 107694529 A CN107694529 A CN 107694529A CN 201711041132 A CN201711041132 A CN 201711041132A CN 107694529 A CN107694529 A CN 107694529A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- attapulgite
- metal ion
- added
- zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000975 dye Substances 0.000 title claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 150000002500 ions Chemical class 0.000 claims abstract description 48
- 239000000047 product Substances 0.000 claims abstract description 34
- 229910001868 water Inorganic materials 0.000 claims abstract description 27
- 229960000892 attapulgite Drugs 0.000 claims description 78
- 229910052625 palygorskite Inorganic materials 0.000 claims description 78
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 47
- 239000006228 supernatant Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 33
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 30
- 239000000499 gel Substances 0.000 claims description 24
- 239000003643 water by type Substances 0.000 claims description 22
- 239000000648 calcium alginate Substances 0.000 claims description 20
- 235000010410 calcium alginate Nutrition 0.000 claims description 20
- 229960002681 calcium alginate Drugs 0.000 claims description 20
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 239000005457 ice water Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 235000010344 sodium nitrate Nutrition 0.000 claims description 16
- 239000004317 sodium nitrate Substances 0.000 claims description 16
- 239000000017 hydrogel Substances 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 8
- 230000008023 solidification Effects 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 16
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 12
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011651 chromium Substances 0.000 abstract description 8
- 229910052804 chromium Inorganic materials 0.000 abstract description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 8
- 239000011133 lead Substances 0.000 abstract description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052753 mercury Inorganic materials 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract description 2
- 238000009434 installation Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 78
- 239000011787 zinc oxide Substances 0.000 description 42
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 34
- 239000000661 sodium alginate Substances 0.000 description 34
- 235000010413 sodium alginate Nutrition 0.000 description 34
- 229940005550 sodium alginate Drugs 0.000 description 34
- 230000008859 change Effects 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229920001661 Chitosan Polymers 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229960001126 alginic acid Drugs 0.000 description 3
- 239000000783 alginic acid Substances 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 150000004781 alginic acids Chemical class 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- -1 lead Chemical class 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B01J35/39—
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of heavy metal ion and the preparation method of organic dyestuff Adsorption type composite aquogel, belong to polymeric material field.Product of the present invention is characterized in that the heavy metal ion such as the nickel that both can effectively remove in water, chromium, lead, mercury, again can photocatalytic degradation so as to removing the organic dyestuff such as light blue, methylene blue.Product of the present invention reaches more than 80% to the eliminating rate of absorption of the heavy metal ion such as low concentration nickel, chromium, lead, mercury in waste water, to the clearance of methylene blue up to more than 85% under natural light action.Prepared by product of the present invention does not need that special installation, industrializing implementation are easy, and product cost is not high.After composite aquogel product absorption heavy metal ion of the present invention, the heavy metal ion that high efficiente callback is adsorbed can be cleaned by cleaning fluid, can disposably wash away more than 95% heavy metal ion adsorbed, gel may be reused.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of to have good inhale to heavy metal ion such as nickel, chromium, lead
Attached remove function and the composite high-molecular hydrogel to organic dyestuff such as light blue, methylene blues simultaneously with good remove function
Preparation method.The composite aquogel both can effectively remove the heavy metal ion such as nickel in water, chromium, lead, mercury, again can photocatalysis
Degrade so as to remove the organic dyestuff such as light blue, methylene blue, and it is high to heavy metal ion in water and organic dyestuff removal efficiency, can
Process field applied to sewage such as electroplating industry, chemical industry.
Background technology
Heavy metal ion pollution produces serious harm to human body.At present, the master of harmless treatment heavy metal ion-containing waste water
Method is wanted to have membrane separation process, electrochemical deposition method, ion-exchange, absorption and biological treatment etc..Wherein, absorption method is to a huge sum of money
Belong to the clearance height of ion, adsorbance is big, and the rate of adsorption is fast, easy to operate.But the adsorbent one of adsorbing heavy metal ions
As price all costly.Therefore, it is modified existing adsorbent developing low-cost with cheap Material cladding and high absorption is imitated
The new adsorbent of rate, it is an important directions of the adsorbent research of adsorbing heavy metal ions.
In recent years, the absorption property of inorganic material heavy metal ion is more and more interested to researchers, wherein concavo-convex
Rod soil (ATP) is exactly most typical a kind of.Attapulgite is a kind of clay of magnesium silicate containing Shuifu County with chain layer structure
Mineral, its special structure make it have very big specific surface area, and physical absorption is very capable.On the other hand, attapulgite band
There is aspect negative electrical charge, there is the cation of interchangeability in Inter layer adsorption so that charge balance, such attapulgite just have
Stronger ionic adsorption exchange capacity.
The present inventor discloses preparation method and its production of a kind of absorbent-type macromolecule composite aquogel in invention early stage
Product (ZL201020595998.1), make carrier, immobilized attapulgite, so as to play concave convex rod well using macromolecule hydrogel
The suction-operated of soil.In addition, disclose the chitin composite flocculant that a kind of heavy metal ionic adsorption amount is big, adsorption efficiency is high
Preparation method and products thereof (CN103274509A), a kind of and preparation method of heavy metal ion adsorbed type composite flocculation agent
And products thereof (CN201611116740.7).The PVDF that the present inventor also discloses absorption heavy metal ion in invention early stage is miscellaneous
Change Flat Membrane ZL201110254106.0, using flat board membrane as carrier, immobilized attapulgite, play attapulgite pair well
The suction-operated of heavy metal ion.
For how by attapulgite be applied to sewage disposal in, exploitation it is a kind of both can be with the heavy metal in efficient absorption water
Ion, again can be with sorbing material problem existing for field quick detection heavy metal.The present inventor discloses one in invention early stage
Kind has the heavy metal ion adsorbed and composite flocculation agent of detection function and preparation method thereof (CN201611117960.1), one kind
The heavy metal ion adsorbed and preparation method of detection type composite aquogel (CN201611116806.2), a kind of heavy metal ion are inhaled
Echo detection type compound water congealing glue fiber and preparation method thereof (CN201611116739.4).Many adsorption materials of invention early stage
Material, heavy metal ion adsorbed ability are greatly improved.
Sodium alginate (SA) is easy to form calcium alginate (CA) gel in ionic calcium soln, and heavy metal ion has well
Absorption property.With calcium alginate gel be carrier coat, fixed attapulgite, its good absorption property and excellent can be made full use of
The characteristics of good formability, the heavy metal ion adsorbed effect of attapulgite is cooperateed with, prepare heavy metal ion adsorbed type gel rubber material.
But trade effluent composition becomes increasingly complex in recent years, outside removing heavy metals ion, contain often while also other difficulties
With the composition of processing, such as organic dyestuff, it has turned into one of the biggest problem in Industrial Wastewater Treatment.Design it is a kind of both had it is good
Removal of heavy metal ions function, the sorbing material that can effectively remove organic dyestuff in water body simultaneously again is still one very big chooses
War.
At present, physical method, chemical method and physical-chemical side are mainly included for organic dyestuff method for governing pollution
Method.Common physical treatment method mainly includes membrane separation process, Bubble-floating Method etc.;Common chemical treatment method mainly has high temperature deep
Spend oxidizing process, photocatalytic oxidation and electrochemical process etc.;Common physical-chemical method mainly includes absorption method, coagulating sedimentation
Method and extraction etc..Photocatalytic degradation method has very big dive as a kind of new technique in terms of organic dye waste water is purified
In advantage.For photochemical catalyst under the conditions of light irradiation, a series of oxidations can be occurred by being adsorbed in the organic pollution of photocatalyst surface
Reduction reaction, and most at last organic pollution oxidation Decomposition into CO2、H2O and some simple inorganic acids, this is for the depollution of environment
For it is significant.
Zinc oxide (ZnO) has good photocatalytic Degradation to organic dyestuff, can reach purification organic dyestuff and give up
The purpose of water, so receiving much concern in recent years.It is ZnO that ZnO, which has the reason for catalytic degradation to organic dyestuff (such as methylene blue),
Under illumination effect, surface can form hole-electron pair, and hole-electron is to further with being adsorbed in the O on ZnO surfaces2And H2O
Reaction generation oxidisability very strong OH and O2 -, OH and O2 -The aromatic rings of methylene blue can be opened, make methylene blue
Molecular structure changes, so as to reach the purpose of degradation of methylene blue.But the intensity of light source, pH value of solution, dye strength, from
Formation of the meeting such as sub- intensity and electronics capturing agent to hole-electron pair impacts, and then can cause shadow to ZnO photocatalysis efficiencies
Ring.Therefore, the photocatalytic Degradation for ZnO to organic dyestuff, how to improve photocatalysis efficiency is still a problem.
The content of the invention
In view of the shortcomings of the prior art, the technical problem that the present invention intends to solve is to provide a kind of adsorbable nickel, chromium, lead, mercury
Etc. heavy metal ion, at the same again can photocatalytic degradation so as to removing the macromolecule Compound Water of the organic dyestuff such as light blue, methylene blue
The preparation method of gel.
Composite aquogel of the present invention is on the basis of calcium alginate/attapulgite composite hydrogel, is introduced to organic
Dyestuff has the ZnO of photocatalytic Degradation and improves the graphene oxide (GO) of ZnO photocatalytic degradation efficiencies, is a kind of marine alga
Sour calcium/attapulgite/ZnO/GO composite aquogels.Composite aquogel of the present invention both can adsorb and go water removal in nickel, chromium, lead
Etc. heavy metal ion, the organic dyestuff such as light blue, methylene blue can be removed with photocatalytic degradation again, and to heavy metal ion in water and
Organic dyestuff removal effect is good, and removal efficiency is high.
It for modifying agent is former that product of the present invention, which uses sodium alginate (SA), attapulgite modified, nano-ZnO and GO,
Material, is cross-linked to form calcium alginate/attapulgite/ZnO/GO hydrogels in ionic calcium soln.ZnO particle diameters of the present invention are
20nm~300nm, described GO are the GO products prepared using improved Hummers methods.
Composite aquogel of the present invention with heavy metal ion and organic dyestuff remove function is made by following methods:
(1) GO preparation:In ice-water bath, 200mL~250mL concentrated sulfuric acids are slowly added into 1L three-necked flask, then
10g~15g graphite and 3g~5g sodium nitrate are sequentially added, the process added must slowly, and preceding graphite passes through instead with sodium nitrate in addition
Multiple grinding, after stirring 1h~1.5h, is then slowly added to 25g~35g potassium permanganate, by it in ice-water bath mechanical agitation 1.5h
~2h.30 DEG C~40 DEG C are then raised temperature to, reacts 2h~2.5h, be then slowly added to 200mL~250mL 30 DEG C~40 DEG C are gone
Ionized water, afterwards reaction system be warming up to 80 DEG C~90 DEG C and stir 10min~20min, then toward being slow added into system
400mL~500mL deionized waters, 20mL~25mL hydrogen peroxide terminating reactions are added after stirring 2min, reactant continues to stir
After 10min~20min, it is centrifuged, and it is multiple with watery hydrochloric acid and deionized water repeated washing, until product pH is 7, i.e.,
Obtain required GO of the invention.
(2) pretreatment of attapulgite:The attapulgite of the mesh of the mesh of 10g~20g particle diameters 300~1000 is weighed, is distilled with 1L
Water washing, its supernatant liquor is taken after to be precipitated, its supernatant liquor is taken after 500rpm centrifugations 1min, a small amount of distillation is added in supernatant liquor
Continue 500rpm centrifugation 1min after water is well mixed, then take its supernatant liquor, after so washing supernatant liquor 3~5 times repeatedly,
Finally it is centrifuged with 4000rpm, takes its precipitation, 24h is dried in vacuo at 90 DEG C, it is corresponding by particle size selection after grinding
The sieve of mesh number, obtain purifying attapulgite.
Configuration concentration is 0.5mol/L~3mol/L hydrochloric acid solution, take 10g~20g purifying attapulgite and 150mL~
200mL hydrochloric acid solutions, which are added in small beaker, to be stirred, and after 5min, heats the mixture to 70 DEG C~80 DEG C, and stirring 1h~
2h, then sonic oscillation 30min~40min, is filtered, and it is to be dried in vacuo 24h at 6,90 DEG C to be washed with distilled water to pH, after grinding
The sieve of corresponding mesh number is selected by particle size, is obtained sour attapulgite modified.
(3) preparation of calcium alginate/attapulgite/ZnO/GO hydrogels:A certain amount of SA is dissolved in 100g deionized waters
In, it is made into the SA solution that concentration is 1%~5%.The attapulgite modified of SA contents 10%~50% is added into SA solution, is stirred
Mix so that attapulgite modified fully dispersed in the solution, obtain gel feed liquid.Weigh the particle diameter 20nm of SA mass 3%~5%
~300nm nano-ZnO, and the GO of ZnO mass 20%~50%, are dispersed in gel solution after being fully ground, and surpass
Sound 2h.Feed liquid is inclined into glass plate, it is quick to immerse 20 DEG C~50 DEG C concentration for 1%~5% with glass bar striking film forming
CaCl2In solution, crosslinking solidification 10h~15h shapings, calcium alginate/attapulgite/ZnO/GO aquagel membranes are obtained.Product is used
Distilled water constantly washs, to remove the Ca of its surface2+, produce composite aquogel of the present invention.
Beneficial effect
Prepared by the present invention is a kind of heavy metal ion and organic dyestuff Adsorption type composite aquogel, using
Blending and method, nickel that the composite aquogel both can adsorb and go in water removal, chromium, the heavy metal ion such as lead, again can be with photocatalysis
Degraded removes the organic dyestuff such as light blue, methylene blue, is a kind of novel alga acid calcium composite aquogel product.
Sodium alginate is easy to form calcium alginate gel in ionic calcium soln, and heavy metal ion has good dispersiveness
Energy.Attapulgite is the good inorganic mineral of a kind of abundance, inexpensive, heavy metal ion adsorbed property, uses calcium alginate gel
For carrier cladding, fixed attapulgite, the characteristics of can making full use of its good absorption property and excellent formability, collaboration is concavo-convex
The heavy metal ion adsorbed effect of rod soil.Nano-ZnO has photocatalytic Degradation, can light containing ZnO in composite aquogel
The organic dyestuff such as catalytic degradation light blue, methylene blue.GO is added in product of the present invention, ZnO photocatalytic degradation effect can be improved
Rate.Therefore, product of the present invention has the function that efficiently heavy-metal ion removal and organic dyestuff simultaneously.
Composite aquogel product of the present invention is equal to the eliminating rate of absorption of the heavy metal ion such as low concentration nickel, chromium, lead, mercury
Reach more than 80%, to the clearance of methylene blue up to more than 85% under natural light action.Plural gel absorption of the present invention
After heavy metal ion, the heavy metal ion that high efficiente callback is adsorbed can be cleaned by cleaning fluid, can disposably wash away more than 95%
The heavy metal ion adsorbed, gel may be reused.
Prepared by the present invention is the composite aquogel with heavy metal ion and organic dyestuff remove function, using
Blending method, compared with prior art, composite aquogel preparation method of the present invention has that technique is simple, does not need special installation, work
Industryization is implemented easy.Product technology hydrogel of the present invention has larger covering amount to attapulgite, so as to which product cost is low, and
Storeroom compatibility is good.
Embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any way
The present invention.
Embodiment 1
(1) GO preparation:In ice-water bath, the 200mL concentrated sulfuric acids are slowly added into 1L three-necked flask, are sequentially added
10g graphite and 3g sodium nitrate, the process added must slowly, and preceding graphite is ground repeatedly with sodium nitrate process in addition, after stirring 1h, is connect
And be slowly added to 25g potassium permanganate, by it in ice-water bath mechanical agitation 1.5h.30 DEG C are then raised temperature to, reacts 2h, it is then slow
Slow 30 DEG C of deionized waters for adding 200mL, afterwards reaction system be warming up to 80 DEG C and stir 10min, then toward delaying again in system
It is slow to add 400mL deionized waters, 20mL hydrogen peroxide terminating reactions are added after stirring 2min, reactant continues after stirring 10min,
It is centrifuged, and it is multiple with watery hydrochloric acid and deionized water repeated washing, until product pH is 7, it is required to produce the present invention
GO。
(2) pretreatment of attapulgite:The attapulgite of the mesh of 10g particle diameters 300 is weighed, distills water washing with 1L, it is to be precipitated
After take its supernatant liquor, take its supernatant liquor after 500rpm centrifugations 1min, in supernatant liquor plus a small amount of distilled water it is well mixed after
Continue 500rpm centrifugation 1min, then take its supernatant liquor, after so washing supernatant liquor 3 times repeatedly, finally entered with 4000rpm
Row centrifuges, and takes its precipitation, 24h is dried in vacuo at 90 DEG C, corresponds to the sieve of mesh number after grinding by particle size selection,
Attapulgite must be purified.
Configuration concentration is 0.5mol/L hydrochloric acid solution, takes 10g purifying attapulgites to be added to 150mL hydrochloric acid solutions small
It is stirred in beaker, after 5min, heats the mixture to 70 DEG C, stir 1h, then sonic oscillation 30min, filter, with distillation
Water washing is to be dried in vacuo 24h at 6,90 DEG C to pH, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains sour change
Property attapulgite.
(3) preparation of calcium alginate/attapulgite/ZnO/GO hydrogels:A certain amount of SA is dissolved in 100g deionized waters
In, it is 1%SA solution to be made into concentration.The attapulgite modified of SA contents 10% is added into SA solution, stirring make it that modification is recessed
Convex rod soil is fully dispersed in the solution, obtains gel feed liquid.The particle diameter for weighing chitosan mass 3% is 20nm nano-ZnO, with
And the GO of ZnO mass 20%, it is dispersed in after being fully ground in gel solution, ultrasonic 2h.Feed liquid is inclined into glass plate, uses glass
Glass rod striking film forming, it is quick to immerse the CaCl that 20 DEG C of concentration are 1%2In solution, crosslinking solidification 10h shaping, obtain calcium alginate/
Attapulgite/ZnO/GO aquagel membranes.Product is constantly washed with distilled water, to remove the Ca of its surface2+, produce institute of the present invention
The composite aquogel stated.
Embodiment 2
(1) GO preparation:In ice-water bath, the 250mL concentrated sulfuric acids are slowly added into 1L three-necked flask, are sequentially added
15g graphite and 5g sodium nitrate, the process added must slowly, and preceding graphite is ground repeatedly with sodium nitrate process in addition, after stirring 1.5h,
Then be slowly added to 35g potassium permanganate, by it in ice-water bath mechanical agitation 2h.40 DEG C are then raised temperature to, reacts 2.5h, then
Be slowly added to 250mL 40 DEG C of deionized waters, reaction system is warming up to 90 DEG C and stirs 20min afterwards, then toward in system again
500mL deionized waters are slowly added to, add 25mL hydrogen peroxide terminating reactions after stirring 2min, reactant continues to stir 20min
Afterwards, it is centrifuged, and it is multiple with watery hydrochloric acid and deionized water repeated washing, until product pH is 7, produce needed for the present invention
GO.
(2) pretreatment of attapulgite:The attapulgite of the mesh of 10g particle diameters 1000 is weighed, distills water washing with 1L, precipitation takes
Its supernatant liquor, 500rpm take its supernatant liquor after centrifuging 1min, continued after adding a small amount of distilled water well mixed in supernatant liquor
500rpm centrifuges 1min, then takes its supernatant liquor, after so washing supernatant liquor 3 times repeatedly, finally with 4000rpm carry out from
The heart separates, and takes its precipitation, 24h is dried in vacuo at 90 DEG C, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains pure
Change attapulgite.
Configuration concentration is 0.5mol/L hydrochloric acid solution, takes 20g purifying attapulgites to be added to 150mL hydrochloric acid solutions small
It is stirred in beaker, after 5min, heats the mixture to 70 DEG C, stir 1h, then sonic oscillation 30min, filter, with distillation
Water washing is to be dried in vacuo 24h at 6,90 DEG C to pH, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains sour change
Property attapulgite.
(3) preparation of calcium alginate/attapulgite/ZnO/GO hydrogels:A certain amount of SA is dissolved in 100g deionized waters
In, it is 2%SA solution to be made into concentration.The attapulgite modified of SA contents 20% is added into SA solution, stirring make it that modification is recessed
Convex rod soil is fully dispersed in the solution, obtains gel feed liquid.The particle diameter for weighing chitosan mass 5% is 300nm nano-ZnO,
And the GO of ZnO mass 50%, it is dispersed in after being fully ground in gel solution, ultrasonic 2h.Feed liquid is inclined into glass plate, used
Glass bar striking film forming, it is quick to immerse the CaCl that 30 DEG C of concentration are 2%2In solution, crosslinking solidification 10h shapings, alginic acid is obtained
Calcium/attapulgite/ZnO/GO aquagel membranes.Product is constantly washed with distilled water, to remove the Ca of its surface2+, produce this hair
Bright described composite aquogel.
Embodiment 3
(1) GO preparation:In ice-water bath, the 200mLL concentrated sulfuric acids are slowly added into 1L three-necked flask, then add successively
Enter 15g graphite and 5g sodium nitrate, the process added must slowly, and preceding graphite is ground repeatedly with sodium nitrate process in addition, stirs 1.5h
Afterwards, be then slowly added to 25g potassium permanganate, by it in ice-water bath mechanical agitation 2h.30 DEG C are then raised temperature to, reacts 2h, with
250mL 30 DEG C of deionized waters are slowly added to afterwards, and reaction system is warming up to 80 DEG C and stirs 10min afterwards, then toward in system
500mL deionized waters are slow added into, add 25mL hydrogen peroxide terminating reactions after stirring 2min, reactant continues to stir
After 20min, it is centrifuged, and it is multiple with watery hydrochloric acid and deionized water repeated washing, until product pH is 7, produce this hair
Bright required GO.
(2) pretreatment of attapulgite:The attapulgite of the mesh of 20g particle diameters 300 is weighed, distills water washing with 1L, precipitation takes
Its supernatant liquor, 500rpm take its supernatant liquor after centrifuging 1min, continued after adding a small amount of distilled water well mixed in supernatant liquor
500rpm centrifuges 1min, then takes its supernatant liquor, after so washing supernatant liquor 5 times repeatedly, finally with 4000rpm carry out from
The heart separates, and takes its precipitation, 24h is dried in vacuo at 90 DEG C, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains pure
Change attapulgite.
Configuration concentration is 3mol/L hydrochloric acid solution, takes 10g purifying attapulgites to be added to small burning with 150mL hydrochloric acid solutions
It is stirred in cup, after 5min, heats the mixture to 80 DEG C, stir 2h, then sonic oscillation 30min, filter, use distilled water
Washing is to be dried in vacuo 24h at 6,90 DEG C to pH, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains sour modification
Attapulgite.
(3) preparation of calcium alginate/attapulgite/ZnO/GO hydrogels:A certain amount of SA is dissolved in 100g deionized waters
In, it is 3%SA solution to be made into concentration.The attapulgite modified of SA contents 30% is added into SA solution, stirring make it that modification is recessed
Convex rod soil is fully dispersed in the solution, obtains gel feed liquid.The particle diameter for weighing chitosan mass 3% is 200nm nano-ZnO,
And the GO of ZnO mass 20%, it is dispersed in after being fully ground in gel solution, ultrasonic 2h.Feed liquid is inclined into glass plate, used
Glass bar striking film forming, it is quick to immerse the CaCl that 40 DEG C of concentration are 3%2In solution, crosslinking solidification 15h shapings, alginic acid is obtained
Calcium/attapulgite/ZnO/GO aquagel membranes.Product is constantly washed with distilled water, to remove the Ca of its surface2+, produce this hair
Bright described composite aquogel.
Embodiment 4
(1) GO preparation:In ice-water bath, the 220mL concentrated sulfuric acids are slowly added into 1L three-necked flask, are sequentially added
12g graphite and 4g sodium nitrate, the process added must slowly, and preceding graphite is ground repeatedly with sodium nitrate process in addition, after stirring 1.5h,
Then be slowly added to 25g potassium permanganate, by it in ice-water bath mechanical agitation 1.5h.35 DEG C are then raised temperature to, reacts 2.5h, with
230mL 35 DEG C of deionized waters are slowly added to afterwards, and reaction system is warming up to 80 DEG C and stirs 10min afterwards, then toward in system
400mL deionized waters are slow added into, add 20mL hydrogen peroxide terminating reactions after stirring 2min, reactant continues to stir
After 10min, it is centrifuged, and it is multiple with watery hydrochloric acid and deionized water repeated washing, until product pH is 7, produce this hair
Bright required GO products.
(2) pretreatment of attapulgite:The attapulgite of the mesh of 15g particle diameters 500 is weighed, distills water washing with 1L, precipitation takes
Its supernatant liquor, 500rpm take its supernatant liquor after centrifuging 1min, continued after adding a small amount of distilled water well mixed in supernatant liquor
500rpm centrifuges 1min, then takes its supernatant liquor, after so washing supernatant liquor 5 times repeatedly, finally with 4000rpm carry out from
The heart separates, and takes its precipitation, 24h is dried in vacuo at 90 DEG C, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains pure
Change attapulgite.
Configuration concentration is 1mol/L hydrochloric acid solution, takes 12g purifying attapulgites to be added to small burning with 180mL hydrochloric acid solutions
It is stirred in cup, after 5min, heats the mixture to 70 DEG C, stir 1h, then sonic oscillation 30min, filter, use distilled water
Washing is to be dried in vacuo 24h at 6,90 DEG C to pH, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains sour modification
Attapulgite.
(3) preparation of calcium alginate/attapulgite/ZnO/GO hydrogels:A certain amount of SA is dissolved in 100g deionized waters
In, it is 3%SA solution to be made into concentration.The attapulgite modified of SA contents 40% is added into SA solution, stirring make it that modification is recessed
Convex rod soil is fully dispersed in the solution, obtains gel feed liquid.The particle diameter for weighing chitosan mass 5% is 100nm nano-ZnO,
And the GO of ZnO mass 40%, it is dispersed in after being fully ground in gel solution, ultrasonic 2h.Feed liquid is inclined into glass plate, used
Glass bar striking film forming, it is quick to immerse the CaCl that 35 DEG C of concentration are 4%2In solution, crosslinking solidification 12h shapings, alginic acid is obtained
Calcium/attapulgite/ZnO/GO aquagel membranes.Product is constantly washed with distilled water, to remove the Ca of its surface2+, produce this hair
Bright described composite aquogel.
Embodiment 5
(1) GO preparation:In ice-water bath, the 220mL concentrated sulfuric acids are slowly added into 1L three-necked flask, are sequentially added
14g graphite and 3g sodium nitrate, the process added must slowly, and preceding graphite is ground repeatedly with sodium nitrate process in addition, stirs 1.25h
Afterwards, be then slowly added to 30g potassium permanganate, by it in ice-water bath mechanical agitation 1.5h.38 DEG C are then raised temperature to, reacts 2h,
220mL 30 DEG C of deionized waters are then slowly added to, reaction system is warming up to 85 DEG C and stirs 10min afterwards, then toward system
In be slow added into 500mL deionized waters, add 25mL hydrogen peroxide terminating reactions after stirring 2min, reactant continues to stir
After 10min, it is centrifuged, and it is multiple with watery hydrochloric acid and deionized water repeated washing, until product pH is 7, produce this hair
Bright required GO products.
(2) pretreatment of attapulgite:The attapulgite of the mesh of 16g particle diameters 800 is weighed, distills water washing with 1L, precipitation takes
Its supernatant liquor, 500rpm take its supernatant liquor after centrifuging 1min, continued after adding a small amount of distilled water well mixed in supernatant liquor
500rpm centrifuges 1min, then takes its supernatant liquor, after so washing supernatant liquor 5 times repeatedly, finally with 4000rpm carry out from
The heart separates, and takes its precipitation, 24h is dried in vacuo at 90 DEG C, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains pure
Change attapulgite.
Configuration concentration is 2.5mol/L hydrochloric acid solution, takes 18g purifying attapulgites to be added to 160mL hydrochloric acid solutions small
It is stirred in beaker, after 5min, heats the mixture to 70 DEG C, stir 2h, then sonic oscillation 40min, filter, with distillation
Water washing is to be dried in vacuo 24h at 6,90 DEG C to pH, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains sour change
Property attapulgite.
(3) preparation of calcium alginate/attapulgite/ZnO/GO hydrogels:A certain amount of SA is dissolved in 100g deionized waters
In, it is 5%SA solution to be made into concentration.The attapulgite modified of SA contents 50% is added into SA solution, stirring make it that modification is recessed
Convex rod soil is fully dispersed in the solution, obtains gel feed liquid.The particle diameter for weighing chitosan mass 3.5% is 200nm nanometer
ZnO, and the GO of ZnO mass 40%, are dispersed in gel solution after being fully ground, ultrasonic 2h.Feed liquid is inclined into glass
Plate, it is quick to immerse the CaCl that 50 DEG C of concentration are 5% with glass bar striking film forming2In solution, crosslinking solidification 15h shapings, sea is obtained
Calcium alginate/attapulgite/ZnO/GO aquagel membranes.Product is constantly washed with distilled water, to remove the Ca of its surface2+, produce
Composite aquogel of the present invention.
Embodiment 6
(1) GO preparation:In ice-water bath, the 240mL concentrated sulfuric acids are slowly added into 1L three-necked flask, are sequentially added
13g graphite and 3.5g sodium nitrate, the process added must slowly, and preceding graphite is ground repeatedly with sodium nitrate process in addition, stirs 1.5h
Afterwards, be then slowly added to 32g potassium permanganate, by it in ice-water bath mechanical agitation 1.8h.38 DEG C are then raised temperature to, reaction
2.5h, 250mL 36 DEG C of deionized waters are then slowly added to, reaction system is warming up to 82 DEG C and stirs 15min afterwards, then past
450mL deionized waters are slow added into system, add 22mL hydrogen peroxide terminating reactions after stirring 2min, reactant continues to stir
After mixing 15min, it is centrifuged, and it is multiple with watery hydrochloric acid and deionized water repeated washing, until product pH is 7, produce this
GO products needed for invention.
(2) pretreatment of attapulgite:The attapulgite of the mesh of 18g particle diameters 1000 is weighed, distills water washing with 1L, precipitation takes
Its supernatant liquor, 500rpm take its supernatant liquor after centrifuging 1min, continued after adding a small amount of distilled water well mixed in supernatant liquor
500rpm centrifuges 1min, then takes its supernatant liquor, after so washing supernatant liquor 5 times repeatedly, finally with 4000rpm carry out from
The heart separates, and takes its precipitation, 24h is dried in vacuo at 90 DEG C, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains pure
Change attapulgite.
Configuration concentration is 3mol/L hydrochloric acid solution, takes 20g purifying attapulgites to be added to small burning with 180mL hydrochloric acid solutions
It is stirred in cup, after 5min, heats the mixture to 75 DEG C, stir 1.5h, then sonic oscillation 35min, filter, with distillation
Water washing is to be dried in vacuo 24h at 6,90 DEG C to pH, by the sieve of the corresponding mesh number of particle size selection after grinding, obtains sour change
Property attapulgite.
(3) preparation of calcium alginate/attapulgite/ZnO/GO hydrogels:A certain amount of SA is dissolved in 100g deionized waters
In, it is 4.2%SA solution to be made into concentration.The attapulgite modified of SA contents 45% is added into SA solution, stirring to be modified
Attapulgite is fully dispersed in the solution, obtains gel feed liquid.The particle diameter for weighing chitosan mass 3.6% is 150nm nanometer
ZnO, and the GO of ZnO mass 35%, are dispersed in gel solution after being fully ground, ultrasonic 2h.Feed liquid is inclined into glass
Plate, it is quick to immerse the CaCl that 35 DEG C of concentration are 4.5% with glass bar striking film forming2In solution, crosslinking solidification 15h shapings, obtain
Calcium alginate/attapulgite/ZnO/GO aquagel membranes.Product is constantly washed with distilled water, to remove the Ca of its surface2+, i.e.,
Obtain composite aquogel of the present invention.
Claims (4)
- A kind of 1. preparation method of heavy metal ion and organic dyestuff Adsorption type composite aquogel, it is characterised in that including Following steps:(1) GO preparation:In ice-water bath, 200mL~250mL concentrated sulfuric acids are slowly added into 1L three-necked flask, then successively 10g~15g graphite and 3g~5g sodium nitrate are added, the process added must slowly, and preceding graphite is ground repeatedly with sodium nitrate process in addition Mill, stir 1h~1.5h after, be then slowly added to 25g~35g potassium permanganate, by its in ice-water bath mechanical agitation 1.5h~ 2h;Then raise temperature to 30 DEG C~40 DEG C, react 2h~2.5h, be then slowly added to 30 DEG C~40 DEG C of 200mL~250mL go from Sub- water, afterwards reaction system be warming up to 80 DEG C~90 DEG C and stir 10min~20min, then toward being slow added into system 400mL~500mL deionized waters, 20mL~25mL hydrogen peroxide terminating reactions are added after stirring 2min, reactant continues to stir After 10min~20min, it is centrifuged, and it is multiple with watery hydrochloric acid and deionized water repeated washing, until product pH is 7, i.e., Obtain required GO of the invention;(2) pretreatment of attapulgite:The attapulgite of the mesh of the mesh of 10g~20g particle diameters 300~1000 is weighed, is distilled and washed with 1L Wash, its supernatant liquor is taken after to be precipitated, its supernatant liquor is taken after 500rpm centrifugations 1min, adds a small amount of distilled water to mix in supernatant liquor Continue 500rpm centrifugation 1min after closing uniformly, then take its supernatant liquor, after so washing supernatant liquor 3~5 times repeatedly, finally It is centrifuged with 4000rpm, takes its precipitation, 24h is dried in vacuo at 90 DEG C, by the corresponding mesh number of particle size selection after grinding Sieve, obtain purifying attapulgite;Configuration concentration is 0.5mol/L~3mol/L hydrochloric acid solution, takes 10g~20g purifying attapulgites and 150mL~200mL Hydrochloric acid solution is added in small beaker and is stirred, and after 5min, heats the mixture to 70 DEG C~80 DEG C, stirs 1h~2h, so Sonic oscillation 30min~40min afterwards, filter, it is to be dried in vacuo 24h at 6,90 DEG C to be washed with distilled water to pH, and grain is pressed after grinding The sieve of the corresponding mesh number of footpath size selection, is obtained sour attapulgite modified;(3) preparation of calcium alginate/attapulgite/ZnO/GO hydrogels:A certain amount of SA is dissolved in 100g deionized waters, matched somebody with somebody Into the SA solution that concentration is 1%~5%;The attapulgite modified of SA contents 10%~50% is added into SA solution, stirring makes Must be attapulgite modified fully dispersed in the solution, obtain gel feed liquid;Weigh the particle diameter 20nm of SA mass 3%~5%~ 300nm nano-ZnO, and the GO of ZnO mass 20%~50%, are dispersed in gel solution after being fully ground, ultrasound 2h;Feed liquid is inclined into glass plate, it is quick to immerse the CaCl that 20 DEG C~50 DEG C concentration are 1%~5% with glass bar striking film forming2 In solution, crosslinking solidification 10h~15h shapings, calcium alginate/attapulgite/ZnO/GO aquagel membranes are obtained;Product distilled water Constantly washing, to remove the Ca of its surface2+, produce composite aquogel of the present invention.
- 2. the preparation method of heavy metal ion as claimed in claim 1 and organic dyestuff Adsorption type composite aquogel, it is special Sign is the nano-ZnO of particle diameter 20nm~300nm of quality 3%~5% in (1), and ZnO mass 20%~50% GO。
- 3. the preparation method of heavy metal ion as claimed in claim 1 and organic dyestuff Adsorption type composite aquogel, it is special Sign is that the attapulgite in (1) is attapulgite modified for acid.
- 4. a kind of heavy metal ion and organic dyestuff Adsorption type composite aquogel, it is characterised in that as described in claim 1 Heavy metal ion and the preparation method of organic dyestuff Adsorption type composite aquogel are prepared.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711041132.9A CN107694529A (en) | 2017-10-30 | 2017-10-30 | A kind of preparation method of heavy metal ion and organic dyestuff Adsorption type composite aquogel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711041132.9A CN107694529A (en) | 2017-10-30 | 2017-10-30 | A kind of preparation method of heavy metal ion and organic dyestuff Adsorption type composite aquogel |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107694529A true CN107694529A (en) | 2018-02-16 |
Family
ID=61177131
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711041132.9A Pending CN107694529A (en) | 2017-10-30 | 2017-10-30 | A kind of preparation method of heavy metal ion and organic dyestuff Adsorption type composite aquogel |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107694529A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109012605A (en) * | 2018-07-16 | 2018-12-18 | 天津师范大学 | A kind of metal organic Hybrid Materials and application with photoelectric effect and characterization of adsorption based on methyl viologen ligand |
CN111763446A (en) * | 2020-07-03 | 2020-10-13 | 中国石油大学(华东) | Strippable hydrogel for removing surface pollutants |
CN115651274A (en) * | 2022-10-31 | 2023-01-31 | 淮阴工学院 | Preparation method of clay-based composite hydrogel for solar seawater desalination |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6790840B1 (en) * | 1999-11-26 | 2004-09-14 | The Regents Of The University Of Michigan | Reversibly cross-linked hydrogels |
CN102658108A (en) * | 2012-05-04 | 2012-09-12 | 东南大学 | Method for preparing photocatalytic filtering membrane based on graphene/semiconductor by an electrospinning method |
CN103349919A (en) * | 2013-07-09 | 2013-10-16 | 福州大学 | Graphene-semiconductor particle compound filter membrane with self-cleaning function |
CN103524674A (en) * | 2013-10-17 | 2014-01-22 | 滁州友林科技发展有限公司 | Method for preparing composite hydrogel for adsorbing heavy metal ions and product thereof |
CN106622156A (en) * | 2016-12-07 | 2017-05-10 | 天津市金鳞水处理科技有限公司 | Preparation method of composite hydrogel for adsorbing and detecting heavy metal ions |
CN107282134A (en) * | 2016-04-12 | 2017-10-24 | 中国科学院上海硅酸盐研究所 | A kind of ZnO photocatalyst of graphene coated and preparation method thereof |
-
2017
- 2017-10-30 CN CN201711041132.9A patent/CN107694529A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6790840B1 (en) * | 1999-11-26 | 2004-09-14 | The Regents Of The University Of Michigan | Reversibly cross-linked hydrogels |
CN102658108A (en) * | 2012-05-04 | 2012-09-12 | 东南大学 | Method for preparing photocatalytic filtering membrane based on graphene/semiconductor by an electrospinning method |
CN103349919A (en) * | 2013-07-09 | 2013-10-16 | 福州大学 | Graphene-semiconductor particle compound filter membrane with self-cleaning function |
CN103524674A (en) * | 2013-10-17 | 2014-01-22 | 滁州友林科技发展有限公司 | Method for preparing composite hydrogel for adsorbing heavy metal ions and product thereof |
CN107282134A (en) * | 2016-04-12 | 2017-10-24 | 中国科学院上海硅酸盐研究所 | A kind of ZnO photocatalyst of graphene coated and preparation method thereof |
CN106622156A (en) * | 2016-12-07 | 2017-05-10 | 天津市金鳞水处理科技有限公司 | Preparation method of composite hydrogel for adsorbing and detecting heavy metal ions |
Non-Patent Citations (1)
Title |
---|
姚超 等: "凹凸棒石/氧化锌纳米复合材料对亚甲基蓝的吸附性能", 《环境科学学报》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109012605A (en) * | 2018-07-16 | 2018-12-18 | 天津师范大学 | A kind of metal organic Hybrid Materials and application with photoelectric effect and characterization of adsorption based on methyl viologen ligand |
CN109012605B (en) * | 2018-07-16 | 2021-09-07 | 天津师范大学 | Metal organic hybrid material based on methyl viologen ligand and having photoelectric effect and adsorption characteristics and application |
CN111763446A (en) * | 2020-07-03 | 2020-10-13 | 中国石油大学(华东) | Strippable hydrogel for removing surface pollutants |
CN115651274A (en) * | 2022-10-31 | 2023-01-31 | 淮阴工学院 | Preparation method of clay-based composite hydrogel for solar seawater desalination |
CN115651274B (en) * | 2022-10-31 | 2024-03-26 | 淮阴工学院 | Preparation method of clay-based composite hydrogel for solar seawater desalination |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Rajoria et al. | Treatment of electroplating industry wastewater: a review on the various techniques | |
Al-Saydeh et al. | Copper removal from industrial wastewater: A comprehensive review | |
Li et al. | Removal of chloride from water and wastewater: removal mechanisms and recent trends | |
Anderson et al. | Treatment of heavy metals containing wastewater using biodegradable adsorbents: A review of mechanism and future trends | |
CN102718544B (en) | Ceramsite for heavy metal wastewater treatment, preparation method and applications thereof | |
CN107088413B (en) | CuO/Cu2O photocatalyst and preparation method and application thereof | |
US20150076070A1 (en) | Advanced treatment method for biochemical tail water of coking wastewater | |
CN107572646A (en) | A kind of composite flocculation agent with heavy metal ion and organic dyestuff remove function and preparation method thereof | |
Yang et al. | Adsorption behavior of cross-linked chitosan modified by graphene oxide for Cu (II) removal | |
CN105399896A (en) | Preparation method of gel material for adsorbing heavy metal ions and phenolic compound and product of gel material | |
CN107694529A (en) | A kind of preparation method of heavy metal ion and organic dyestuff Adsorption type composite aquogel | |
CN102452753A (en) | Saliferous organic wastewater treatment method | |
CN103524674A (en) | Method for preparing composite hydrogel for adsorbing heavy metal ions and product thereof | |
CN103480347A (en) | Preparation method of composite flat membrane for adsorbing heavy metal ions and product thereof | |
CN109052543B (en) | Method for recovering precious metal silver in wastewater | |
CN106745591A (en) | A kind of preparation method of heavy metal ion adsorbed type composite flocculation agent and products thereof | |
CN107381949B (en) | A kind of processing method of oil-containing heavy metal wastewater thereby | |
Shaikh | Adsorption of Pb (II) from wastewater by natural and synthetic adsorbents | |
CN103861564B (en) | Preparation based on the graphene oxide adsorbing material that dendrimer is modified | |
Itankar et al. | Assessing physicochemical technologies for removing hexavalent chromium from contaminated waters—An overview and future research directions | |
Krstić | Some effective methods for treatment of wastewater from Cu production | |
Nezhadnaderi | Comparison of the application of Heavy metals adsorption methods from aqueous solutions for development of sustainable environment | |
CN107626219A (en) | A kind of antipollution hollow-fibre membrane of heavy metal ion and organic dyestuff remove function | |
CN109092360A (en) | A kind of preparation method of the nano hybridization gel mould for catalytic degradation organic matter | |
CN106745592B (en) | It is a kind of with heavy metal ion adsorbed and detection function composite flocculation agent and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180216 |