CN107915803A - It is a kind of to prepare the method for removing cadmic nano-composite gel in waste water - Google Patents
It is a kind of to prepare the method for removing cadmic nano-composite gel in waste water Download PDFInfo
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- CN107915803A CN107915803A CN201710992186.7A CN201710992186A CN107915803A CN 107915803 A CN107915803 A CN 107915803A CN 201710992186 A CN201710992186 A CN 201710992186A CN 107915803 A CN107915803 A CN 107915803A
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- clinoptilolite
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- waste water
- cadmic
- composite gel
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 24
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910001603 clinoptilolite Inorganic materials 0.000 claims abstract description 47
- 229920001661 Chitosan Polymers 0.000 claims abstract description 42
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims abstract description 33
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 235000019394 potassium persulphate Nutrition 0.000 claims description 12
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000003463 adsorbent Substances 0.000 abstract description 8
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 abstract description 5
- 229920005615 natural polymer Polymers 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229920000578 graft copolymer Polymers 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003795 desorption Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000017 hydrogel Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- -1 Pb2+And Cd2+ Chemical class 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
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- 238000010668 complexation reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000009514 concussion Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- 239000002594 sorbent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
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- 102000008186 Collagen Human genes 0.000 description 1
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- 241000196324 Embryophyta Species 0.000 description 1
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- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000018729 macromolecule modification Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0069—Post treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of method for preparing and removing cadmic nano-composite gel in waste water：Using hydroxyethyl chitosan and clinoptilolite as raw material, reacted by free radical grafting copolymerization by acrylamide graft to hydroxyethyl chitosan macromolecule, and mixed with clinoptilolite, product is cleaned, after drying, ball milling is carried out, obtains nanoscale clinoptilolite/hydroxyethyl chitosan graft copolymer plural gel；The nano-composite gel adsorbent obtained by this method is in gray powdery, efficiently remove the divalent cadmium ion in waste water, it is and environmentally safe, it is environmentally protective, the method of the present invention can not only improve the comprehensive utilization ratio of the natural polymers such as chitosan derivatives, clinoptilolite, but also be Cd in heavy metal wastewater thereby2+Efficient absorption removing provides a feasible program, and application prospect is broader.
Description
Technical field
The present invention relates to one kind to prepare with selective absorption divalent cadmium ion（Cr2+）Clinoptilolite/ethoxy shell gather
The method of sugared graft copolymer nano-composite gel, belongs to natural macromolecule modification field of material technology.
Background technology
With industrial high speed development, the waste water containing many potential toxic metals is largely released to earth's surface and underground water
In, water pollution problems is increasingly subject to the concern of people.In these industry, mineral products and metallurgy industry are played the part of in water resource pollution
Dominant role, they lose not only directly by the discharging of waste liquid containing heavy metal ion into fluvial system into environment
Abandon the undressed solid waste containing kish.The solid wastes such as slag are toppled in the environment, over time,
Heavy metal ion still can be moved to constantly in surface water and groundwater.Some heavy metal ion such as Pb2+And Cd2+, even in phase
It can also have a negative impact to relatively low concentration to community of aquatic organism and human health.These heavy metal ion are to from environment
Middle removal needs develop effective and sustainable technical solution.The skill of some heavy-metal ion removals obtained for many years
Art, for example, chemical precipitation method, oxidation-reduction method, osmosis, electrolysis etc., but effect is not apparent.Because these methods
It is not using high cost as cost is removed, can exactly forms new solid waste byproduct.In numerous processing methods, adsorption technology
Have become one of research hotspot of heavy metals removal.
Many adsorbents have been successfully applied to remove the metal ion in waste water, but since biomass adsorbent is unique
Property such as biological degradability, low cost and abundant availability, it is typically what is be preferred.Biomass adsorbent due to
It is enriched with raw material sources, wide in variety, and cost is low, at low concentrations high treating effect, and adsorption capacity is big, and speed is fast, selection
Property it is good, adsorption plant is simple, it is easy to operate the features such as, have broad application prospects in water removal is gone in terms of heavy metal.Biomass is inhaled
Attached dose of raw material include colloid, collagen, cellulose, alginates, carrageenan and chitosan.Based on biomass polymers
Obtained hydrogel, its absorption behavior can be by mixing any other exotic material such as metal oxide, zeolite or clay
Improve Deng nano particle.Natural zeolite is cheap, resource reserve is big, its huge specific surface area and excellent ion exchange
Absorption property has a wide range of applications in field of waste water treatment.Some natural zeolites and clay such as bentonite and tiltedly hair boiling
Stone is cheap, is widely used in Water warfare application.
Zeolite may be considered one kind by a certain number of Al3+Substitute Si4+The porous sial of the water-bearing structure formed
Hydrochlorate mineral matter.Usual zeolite is oxygen-octahedron and Al3+Substitute Si4+The aluminum-oxygen tetrahedron structure formed afterwards, i.e., it is former with silicon
Son or aluminium atom are tetrahedron center, are around surrounded by 4 oxygen atoms.Since aluminium atom is in+trivalent, have in aluminum-oxygen tetrahedron
The valence electron of one oxygen atom is not neutralized, and it is in -1 valency state to make it.In order to keep its overall electrical neutralization, its four sides
Surrounding must have a cation with nominal price（Cation is typically Na+、K+、1/2Ca2+）.These cations and aluminosilicate
It is weaker with reference to power, therefore there is very big mobility, ion exchange easily occurs with the cation in aqueous solution around.
It has larger electrostatic attraction and a stronger ion exchangeable to this structures shape of zeolite, therefore zeolite is to heavy metal
Removal may include a variety of effects.The research of Jenne etc. shows：Zeolite the cutting mechanisms of heavy metal ion are mainly included from
Son exchanges and chemisorption.Wherein ion exchange may include 2 kinds of forms：Metal ion and zeolite surface hydroxy functional group
In proton exchange；Metal ion has the cation of stronger mobility with zeolite surface（Na+、K+、Ca2+Deng）Hand over
Change.There are chemisorption, chemisorbed to generally include table for the complex reaction that heavy metal ion and zeolite surface hydroxyl occur
Face complexing and inner complexation effect.Acted on compared to surface complexation, it is generally recognized that inner complexation effect is more stablized, and is boiled
Combination between stone and heavy metal ion is even closer.Strong active site present on the screening molecular property of zeolite and its surface
Them are made to be highly suitable for adsorbing different types of Wastewater Pollutant.The natural minerals that clinoptilolite is made of alumino-silicate
Matter, can mix the matrix cation of various metal oxides and metal, be usually used in adsorbing dyestuff from different waste water and again
Metal ion.
Chitosan is a kind of natural polymer alkaline polysaccharide, have the characteristics that it is nontoxic, nonirritant, without challeng,
With good biocompatibility and biodegradability, it is widely used in food, medicine and other fields.However, due to intermolecular
The strong hydrogen bond action with intramolecular, chitosan can only be dissolved in a small number of dilute acid solns such as spirit of vinegar；Meanwhile its degradation speed
It is relatively slow, it is difficult to match with regeneration speed, easily causes " tissue defects ", therefore, its application is greatly limited.Gather in shell
Hydroxyl or amino groups in saccharide ring are suitably introduced into hydroxyethyl groups, have effectively slackened between chitosan molecule or interior this hydrogen
Key acts on, and is conducive to improve the solubility property of chitosan, strengthens its follow-up modification power.
Since heavy metal adsorption type gel depends on synthesis class or semi-synthetic family macromolecule, it is for full-natural material
The exploitation of the gel of matrix is also without the support of enough bases and technology, therefore environmentally friendly, selective absorption gel is also
The industry of non-scale utilizes and exploitation.
The content of the invention
It is an object of the invention to provide a kind of method for preparing and removing cadmic nano-composite gel in waste water, this is received
Rice plural gel efficient selective removes divalent cadmium ion in waste water, and the method for the present invention is mainly reacted by free radical grafting copolymerization
By on acrylamide graft to hydroxyethyl chitosan macromolecular scaffold, and mixed with clinoptilolite, formed nanoscale clinoptilolite/
Hydroxyethyl chitosan graft copolymer plural gel, for Cd in adsorption aqueous solution2+Ion, the method for the present invention can not only improve
The comprehensive utilization ratio of the natural polymers such as chitosan derivatives, clinoptilolite, and be Cd in heavy metal wastewater thereby2+Efficient absorption
Removing provides a feasible program.
Technical scheme is as follows：Deionized water is added in clinoptilolite powder first, sonic oscillation is uniform to be obtained
To clinoptilolite dispersion liquid, then into hydroxyethyl chitosan solution, clinoptilolite dispersion liquid, potassium peroxydisulfate are sequentially added（Letter
Claim KPS）, N,N methylene bis acrylamide（Abbreviation MBA）, nitrogen is led to after being mixed, then adds acrylamide（Abbreviation AAm）,
Stir evenly, graft copolymerization carried out at 45 ~ 80 DEG C, after the reactant of generation is cooled to room temperature, successively with hot water and
Acetone rinses repeatedly and drying, then carries out ball mill grinding, obtains nano-composite gel.
The present invention prepares the method for removing cadmic nano-composite gel in waste water, and concrete operations are as follows：
（1）Clinoptilolite powder is weighed, deionized water is added, then carries out sonic oscillation, make clinoptilolite powder dispersed
In deionized water, obtain clinoptilolite dispersion liquid, the wherein power of sonic oscillation is 500 ~ 2000W, duration of oscillation for 0.5 ~
5.0h, the wherein concentration of clinoptilolite dispersion liquid are 0.1 ~ 10mg/mL；
（2）Hydroxyethyl chitosan solid is weighed, deionized water is added and is made into hydroxyethyl chitosan solution, then gather to ethoxy shell
Clinoptilolite dispersion liquid, potassium peroxydisulfate are sequentially added in sugar juice（KPS）And N, N- methylene-bisacrylamide, stirring are mixed,
Nitrogen is then passed to, after leading to 10 ~ 30min of nitrogen, adds acrylamide, and graft copolymerization, wherein hydroxyl are carried out at 45 ~ 80 DEG C
The concentration of ethyl chitosan solution is 0.01 ~ 0.1g/mL, wherein the volume of clinoptilolite dispersion liquid and hydroxyethyl chitosan solution
Than for 1:10~10:1, potassium peroxydisulfate, N, the quality of N- methylene-bisacrylamides and acrylamide and hydroxyethyl chitosan solid
Than being respectively 0.05 ~ 0.5,0.03 ~ 0.1 and 0.5 ~ 5, the graft copolymerization time is 1 ~ 10h；
（3）By step（2）Reaction product be cooled to room temperature after, cleaned repeatedly with hot water and acetone successively and dry, then
Ball mill grinding is carried out, it is 35 ~ 55 DEG C, wherein ball to obtain removing cadmic nanoscale plural gel wherein drying temperature in waste water
It is solvent that trimethylbenzene is added when being milled broken, and the ball mill grinding time is 24 ~ 120h.
It is in gray powdery by nano-composite gel adsorbent made from the method for the present invention.
Advantages of the present invention and technique effect：
（1）The present invention prepares selective absorption Cd using hydroxyethyl chitosan and clinoptilolite as raw material2+The nanometer blending of ion is multiple
Gel is closed, can efficiently remove the divalent cadmium ion in waste water, and it is environmentally safe, it is environmentally protective；
（2）The method of the present invention can not only improve the comprehensive utilization ratio of the natural polymers such as chitosan derivatives, clinoptilolite, and
And it is Cd in heavy metal wastewater thereby2+Efficient absorption removing provides a feasible program.
Embodiment
The present invention is described in further detail with reference to embodiment, but the scope of the present invention is not limited in described
Hold.
Embodiment 1：The method for removing cadmic nano-composite gel in waste water is prepared, concrete operations are as follows：
（1）The dispersion process of clinoptilolite
0.1mg clinoptilolite powder is weighed, adds 1mL deionized waters, compound concentration is the clinoptilolite dispersion liquid of 0.1mg/mL,
Be then placed in ice-water bath, using ultrasonic generator under the power of 500W ultrasound 0.5h, make clinoptilolite dispersed
In deionized water；
（2）Composite hydrogel realizes process
1g hydroxyethyl chitosans are dissolved in 100mL deionized waters, compound concentration is that the hydroxyethyl chitosan of 0.01g/mL is molten
Liquid, then sequentially adds clinoptilolite dispersion liquid, potassium peroxydisulfate 0.05g and N, N- di-2-ethylhexylphosphine oxide into hydroxyethyl chitosan solution
Acrylamide 0.03g, dissolves and mixes, then pass to nitrogen, after leading to nitrogen 10min, 0.5g acrylamides is added, in 45 DEG C of conditions
The volume ratio of lower progress graft copolymerization 1h, wherein clinoptilolite dispersion liquid and hydroxyethyl chitosan solution is 10:1, over cure
Sour potassium, N,N methylene bis acrylamide and acrylamide and the mass ratio of hydroxyethyl chitosan solid are respectively 0.05,0.03
With 0.5；
（3）The preparation process of nano adsorption gel
By step（2）The reactant of generation is cooled to 23 DEG C, is washed repeatedly 3 times with hot water and acetone successively, is placed in 35 DEG C of baking ovens
Interior drying, dried object obtain clinoptilolite/hydroxyethyl chitosan grafting using trimethylbenzene as solvent ball mill attrition grinding 24h
Copolymer nano plural gel.
（4）The character of nano-composite gel
Above-mentioned gel sample is put in the Cr that concentration is 1000mg/L2+Concussion absorption 24h, utilizes plasma photoelectricity in solution
It is 9.98mg/g that direct-reading spectrometer, which measures the sample adsorption capacity,.
（5）The desorption of hydrogel and recycle process
Initially carry out absorption-desorption test 5 circulation, adsorption of metal ions on the sorbent, then 50mL0.1mol/L's
24h is desorbed in HCl solution.After desorption, using the avtive spot of the NaOH solution reproducing adsorbent of 1mol/L, then it is re-used for
Next sorption cycle.After above-mentioned 5 times recycle, the adsorption capacity of gel is 5.83mg/g.
Embodiment 2：The method for removing cadmic nano-composite gel in waste water is prepared, concrete operations are as follows：
（1）The dispersion process of clinoptilolite
10mg clinoptilolite powder is weighed, adds 1mL deionized waters, compound concentration is the clinoptilolite dispersion liquid of 10mg/mL, so
After be put into ice-water bath, using ultrasonic generator under the power of 2000W ultrasound 5h, be dispersed in clinoptilolite
In ionized water；
（2）Composite hydrogel realizes process
1g hydroxyethyl chitosans are dissolved in 10mL deionized waters, compound concentration is the hydroxyethyl chitosan solution of 0.1g/mL,
Then clinoptilolite dispersion liquid, 0. 5g of potassium peroxydisulfate and N, N- di-2-ethylhexylphosphine oxide third are sequentially added into hydroxyethyl chitosan solution
Acrylamide 0.1g, dissolves and mixes, then pass to nitrogen, after leading to nitrogen 30min, adds 5g acrylamides, under the conditions of 60 DEG C into
The volume ratio of row graft copolymerization 10h, wherein clinoptilolite dispersion liquid and hydroxyethyl chitosan solution is 5:1, potassium peroxydisulfate,
The mass ratio of N,N methylene bis acrylamide and acrylamide and hydroxyethyl chitosan solid is respectively 0. 5,0.1 and 5；
（3）The preparation process of nano adsorption gel
By step（2）The reactant of generation is cooled to 25 DEG C, is washed repeatedly 6 times with hot water and acetone successively, is placed in 55 DEG C of baking ovens
Interior drying, dried object obtain clinoptilolite/hydroxyethyl chitosan grafting using trimethylbenzene as solvent ball mill attrition grinding 120h
Copolymer nano plural gel.
（4）The character of nano-composite gel
Above-mentioned gel sample is put in the Cr that concentration is 1000mg/L2+Concussion absorption 24h, utilizes plasma photoelectricity in solution
It is 27.38mg/g that direct-reading spectrometer, which measures the sample adsorption capacity,.
（5）The desorption of hydrogel and recycle process
Initially carry out absorption-desorption and test 5 circulations；Adsorption of metal ions on the sorbent, then 50ml0.1mol/L's
24h is desorbed in HCl solution.After desorption, using the avtive spot of the NaOH solution reproducing adsorbent of 1mol/L, then it is re-used for
Next sorption cycle.After above-mentioned 5 times recycle, the adsorption capacity of gel is 20.36mg/g.
Embodiment 3：The method for removing cadmic nano-composite gel in waste water is prepared, concrete operations are as follows：
（1）The dispersion process of clinoptilolite
5mg clinoptilolite powder is weighed, adds 1mL deionized waters, compound concentration is the clinoptilolite dispersion liquid of 5mg/mL, then
Be put into ice-water bath, using ultrasonic generator under the power of 1500W ultrasound 2.5h, be dispersed in clinoptilolite
In ionized water；
（2）Composite hydrogel realizes process
1g hydroxyethyl chitosans are dissolved in 20mL deionized waters, compound concentration is that the hydroxyethyl chitosan of 0.05g/mL is molten
Liquid, then sequentially adds clinoptilolite dispersion liquid 1mL, potassium peroxydisulfate 0.25g and N, N- methylene into hydroxyethyl chitosan solution
Base bisacrylamide 0.05g, dissolves and mixes, then pass to nitrogen, after leading to nitrogen 15min, 2.5g acrylamides is added, at 80 DEG C
Under the conditions of carry out graft copolymerization 5h, the wherein volume ratio of clinoptilolite dispersion liquid and hydroxyethyl chitosan solution is 1:10,
The mass ratio of potassium peroxydisulfate, N,N methylene bis acrylamide and acrylamide and hydroxyethyl chitosan solid is respectively 0.25,
0.05 and 2.5；
（3）The preparation process of nano adsorption gel
By step（2）The reactant of generation is cooled to 24 DEG C, is washed 5 times with hot water and acetone successively, is placed in 45 DEG C of baking ovens and does
Dry, dried object obtains clinoptilolite/hydroxyethyl chitosan graft copolymerization using trimethylbenzene as solvent ball mill attrition grinding 60h
Thing nano-composite gel.
（4）The character of nano-composite gel
Above-mentioned gel sample is put in the Cr that concentration is 1000mg/L2+Concussion absorption 24h, utilizes plasma photoelectricity in solution
It is 21.57mg/g that direct-reading spectrometer, which measures the sample adsorption capacity,.
（5）The desorption of hydrogel and recycle process
Initially carry out absorption-desorption and test 5 circulations;Adsorption of metal ions on the sorbent, then 50ml0.1mol/L's
24h is desorbed in HCl solution.After desorption, using the avtive spot of the NaOH solution reproducing adsorbent of 1mol/L, then it is re-used for
Next sorption cycle.After above-mentioned 5 times recycle, the adsorption capacity of gel is 16.19mg/g.
Claims (8)
1. a kind of prepare the method for removing cadmic nano-composite gel in waste water, it is characterised in that carries out as follows：
（1）Clinoptilolite powder is weighed, deionized water is added, then carries out sonic oscillation, make clinoptilolite powder dispersed
In deionized water, clinoptilolite dispersion liquid is obtained；
（2）Hydroxyethyl chitosan solid is weighed, deionized water is added and prepares hydroxyethyl chitosan solution, then gather to ethoxy shell
Clinoptilolite dispersion liquid, potassium peroxydisulfate and N, N- methylene-bisacrylamide are sequentially added in sugar juice, stirring is passed through after being mixed
Nitrogen, after leading to 10 ~ 30min of nitrogen, adds acrylamide, and graft copolymerization is carried out at 45 ~ 80 DEG C, and wherein ethoxy shell gathers
The concentration of sugar juice is 0.01 ~ 0.1g/mL, and the volume ratio of clinoptilolite dispersion liquid and hydroxyethyl chitosan solution is 1:10~10:
1, potassium peroxydisulfate, N, N- methylene-bisacrylamides and the mass ratio of acrylamide and hydroxyethyl chitosan solid are respectively 0.05
~ 0.5,0.03 ~ 0.1 and 0.5 ~ 5；
（3）By step（2）Reaction product be cooled to room temperature after, cleaned and dried with hot water and acetone successively, then carried out
Ball mill grinding, obtains removing cadmic nanoscale plural gel in waste water.
2. according to claim 1 prepare the method for removing cadmic nano-composite gel in waste water, it is characterised in that：
Step（1）The concentration of clinoptilolite dispersion liquid is 0.1 ~ 10mg/mL.
3. according to claim 1 prepare the method for removing cadmic nano-composite gel in waste water, it is characterised in that：
Step（1）The power of sonic oscillation is 500 ~ 2000W, and duration of oscillation is 0.5 ~ 5.0h.
4. according to claim 1 prepare the method for removing cadmic nano-composite gel in waste water, it is characterised in that：
Step（2）The graft copolymerization time is 1 ~ 10h.
5. according to claim 1 prepare the method for removing cadmic nano-composite gel in waste water, it is characterised in that：
Step（3）Middle drying temperature is 35 ~ 55 DEG C.
6. according to claim 1 prepare the method for removing cadmic nano-composite gel in waste water, it is characterised in that：
Step（3）It is solvent that trimethylbenzene is added during ball mill grinding.
7. according to claim 1 prepare the method for removing cadmic nano-composite gel in waste water, it is characterised in that：
Step（3）The ball mill grinding time is 24 ~ 120h.
8. according to claim 1 prepare the method for removing cadmic nano-composite gel in waste water, it is characterised in that：
Step（3）Wash number is 3 ~ 6 times.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111715193A (en) * | 2020-07-02 | 2020-09-29 | 武汉大学 | Analcime/chitosan composite material, preparation method thereof and application of analcime/chitosan composite material as heavy metal adsorption material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020143081A1 (en) * | 2001-01-16 | 2002-10-03 | Pei Li | Amphiphilic core-shell latexes |
| CN101302273A (en) * | 2008-06-30 | 2008-11-12 | 重庆大学 | Preparation of chitose-acrylic amide graft copolymerization flocculant |
| CN102675540A (en) * | 2011-03-15 | 2012-09-19 | 中南林业科技大学 | Heavy metal ion adsorption resin and preparation method thereof |
| CN105056911A (en) * | 2015-08-05 | 2015-11-18 | 珠海国佳新材股份有限公司 | Heavy metal adsorption gel material and environment embattling treatment method |
| CN105709704A (en) * | 2016-02-03 | 2016-06-29 | 西北师范大学 | Preparation of chitosan-based adsorption agent and application of chitosan-based adsorption agent to heavy metal ion wastewater treatment |
| CN106188442A (en) * | 2016-08-02 | 2016-12-07 | 西安交通大学 | A kind of chitosan derivatives hydrogel and preparation method thereof |
| CN106311188A (en) * | 2016-09-18 | 2017-01-11 | 西北师范大学 | Chitosan/palygorskite/polyacrylamide composite hydrogel preparation method |
-
2017
- 2017-10-23 CN CN201710992186.7A patent/CN107915803B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020143081A1 (en) * | 2001-01-16 | 2002-10-03 | Pei Li | Amphiphilic core-shell latexes |
| CN101302273A (en) * | 2008-06-30 | 2008-11-12 | 重庆大学 | Preparation of chitose-acrylic amide graft copolymerization flocculant |
| CN102675540A (en) * | 2011-03-15 | 2012-09-19 | 中南林业科技大学 | Heavy metal ion adsorption resin and preparation method thereof |
| CN105056911A (en) * | 2015-08-05 | 2015-11-18 | 珠海国佳新材股份有限公司 | Heavy metal adsorption gel material and environment embattling treatment method |
| CN105709704A (en) * | 2016-02-03 | 2016-06-29 | 西北师范大学 | Preparation of chitosan-based adsorption agent and application of chitosan-based adsorption agent to heavy metal ion wastewater treatment |
| CN106188442A (en) * | 2016-08-02 | 2016-12-07 | 西安交通大学 | A kind of chitosan derivatives hydrogel and preparation method thereof |
| CN106311188A (en) * | 2016-09-18 | 2017-01-11 | 西北师范大学 | Chitosan/palygorskite/polyacrylamide composite hydrogel preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111715193A (en) * | 2020-07-02 | 2020-09-29 | 武汉大学 | Analcime/chitosan composite material, preparation method thereof and application of analcime/chitosan composite material as heavy metal adsorption material |
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