CN107952416A - A kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal and preparation method thereof - Google Patents
A kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal and preparation method thereof Download PDFInfo
- Publication number
- CN107952416A CN107952416A CN201711182044.0A CN201711182044A CN107952416A CN 107952416 A CN107952416 A CN 107952416A CN 201711182044 A CN201711182044 A CN 201711182044A CN 107952416 A CN107952416 A CN 107952416A
- Authority
- CN
- China
- Prior art keywords
- oyster shell
- shell whiting
- microsphere
- heavy metal
- preparation
- 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.)
- Granted
Links
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
- B01J20/28—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
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal and preparation method thereof, and Chitosan powder and the weight ratio of oyster shell whiting are 1 in complex microsphere:0.3‑0.45.Its preparation method is：By shell acid soak, clean, dry, calcining, grinds to obtain thick oyster shell whiting；Crush to obtain nanometer oyster shell whiting；Chitosan powder and oyster shell whiting drop are molded, it is cross-linking modified, clean up, dry to obtain complex microsphere；Complex microsphere is added to containing in thiocarbamide and epoxychloropropane solution, reacts to obtain complex microsphere product.Complex microsphere of the present invention combines the advantage of oyster shell whiting and chitosan, and the addition of oyster shell whiting not only increases the mechanical stability of chitin carrier, but also can improve the complexing power of carrier and transition metal, it can be achieved that the recycling of heavy metal；Microballoon prepared by preparation method of the present invention has high monodispersity, and microspherulite diameter size, pattern, particle diameter and component are controllable, uniform particle sizes, high mechanical strength.
Description
Technical field
It is compound more particularly, to a kind of oyster shell whiting chitosan for adsorbing heavy metal the present invention relates to environment-friendly materials technical field
Microballoon and preparation method thereof.
Background technology
With expanding economy, the huge sum of money that is produced in the industrial processes such as mining and metallurgy, machine-building, chemical industry, electronics, instrument
Belong to waste water（Contain the heavy metal ion such as chromium, cadmium, copper, mercury, nickel, zinc）It is to water pollution most serious and maximum to mankind's harm
One of industrial wastewater.Heavy metal in waste water is that various common method for treating water cannot decompose destruction, and can only shift them
Existence position and change their physical and chemical state.Therefore, heavy metal wastewater thereby should produce place treatment in situ, different
Other waste water mix.If by the use of the sludge and waste water for containing heavy metal ion as fertilizer and irrigated farmland, soil can be made to get dirty
Dye, causes to cause the enrichment of heavy metal ion in aquatile in crops and after entrance water body, human body is produced by food chain
It is raw to seriously endanger.The 1960s, world-shaking Japanese nuisance disease-minamata disease and itai-itai, was exactly respectively by mercury-containing waste water
Caused by cadmium wastewater polluted-water.Processing effluent containing heavy metal ions technology have at present chemical precipitation method, electrochemical process,
Absorption method and membrane separation process etc.；Also some new technologies such as nanometer technology, photocatalytic method, New Type of Mesoporous material and gene processing
Technology etc..Wherein using environmentally protective, cheap natural adsorbent administer heavy metal pollution in wastewater be even more in recent years by
To common concern.
With exploitation of the people for shellfish software part, substantial amounts of waste shell resource is caused, these shells are a large amount of
Heap comes, and fails to be effectively utilized, and remaining soft tissue occurs putrid and deteriorated so as to produce a series of to have on shell
The harmful material of poison, so as to cause inevitably to injure to environment, oyster shell whiting is used, and is conducive to administer getting worse
Problem of environmental pollution.The main component of oyster shell whiting is the calcified material such as calcium carbonate, calcium containing small amounts, calcium hydroxide, itself
It is porous fibrous double helix construction structure again, high intensity, porosity, the micro-nano skeleton structure of Mussel shell has porosity, ruler
Very little to can be controlled between 100 nanometers to 5 microns, oyster shell whiting itself just has good adsorption effect to heavy metal.In addition, micro-nano
The meter ruler cun usually display material more identical than normal size has the reactivity and adsorption capacity of higher, and nanometer technology is gradual
Applied in sewage treatment field.But the research for nanometer shell powder composite material in terms of sewage disposal is also seldom.
Chitosan be chitosan moiety it is deacetylated after product, by its abundant functional group's composition, biocompatibility, life
Biodegradable and nontoxicity, chitosan have many materials chelating suction-operated, amino in its molecule and with amino phase
The hydroxyl faced and many metal ions（Such as Hg2+、Ni2+、Cu2+、pb2+、CA2+、Ag+Deng）Stable chelate can be formed, for controlling
Manage heavy metal wastewater thereby, purification tap water and separating metal ions etc. in hydrometallurgy.Japan is to be administered earliest using chitosan
The country of waste water, per annual consumption up to 500 tons；U.S.EPA also approved by chitosan be used for drinking water purifying.In addition, shell
Glycan can adsorb dyestuff, protein, amino acid, nucleic acid, enzyme, halogen etc., used by complexing and the effect of ion exchange
In the processing of waste water from dyestuff, dyeing waste water, food industrial wastewater, so that environment purification, protects human health.However, chitosan
Proportion and mechanical strength it is relatively low and unstable to soda acid, these shortcomings limit its application popularization.To improve shell
The performance of glycan, can be fixed on inorganic matter and prepare organo-mineral complexing adsorbent.Shell is a kind of organic-inorganic
Compound biomineralization material, calcium carbonate accounts for 95% during it is formed, remaining 5% is the organic matters such as protein and polysaccharide, this spy
Different structure makes shell powder innately have preferable organic compatibility.Utilize the heavy water-based energy of oyster shell whiting itself in water, absorption
Go the oyster shell whiting chitosan composite micro-nano rice ball of removing heavy metals to can be good at being separated from the water by precipitating filtering, recycle.
The content of the invention
It is an object of the present invention to providing a kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, this is compound micro-
Ball has higher adsorption capacity and the faster rate of adsorption, and it is strong to adsorb the ability of heavy metal, has antibiotic property, repeats and utilizes
Property is strong, and stronger adsorption capacity is still shown after 6 adsorption-desorption cycles are undergone.
It is an object of the present invention to provide a kind of preparation method of oyster shell whiting chitosan compound microsphere, the preparation method
It is molded and cross-linking modified, chitosan is fixed on oyster shell whiting so that the microballoon of preparation has high monodispersity, micro- with reference to drop
Ball particle size, pattern, particle diameter and component are controllable, uniform particle sizes, high mechanical strength.
The present invention is directed to the problem of being mentioned in above-mentioned technology, and the technical solution taken is：
A kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, Chitosan powder and the weight ratio of oyster shell whiting in complex microsphere
For 1:0.3-0.45, the diameter of complex microsphere is for 0.4-0.6mm.Above-mentioned complex microsphere is with higher adsorption capacity and faster
The rate of adsorption, adsorb that the ability of heavy metal is strong, be incorporated into the chemistry of electronics transfer in adsorption process and occupy leading position,
It can be good at being separated from the water by precipitating filtering after heavy metal, recycle for adsorbing, it is strong to repeat usability, is passing through
Stronger adsorption capacity is still shown after going through 6 adsorption-desorption cycles, while the complex microsphere has certain antibiotic property,
During for handling heavy metal wastewater thereby, it is not necessary to additionally add antiseptic.
A kind of preparation method for the oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, including prepared by thick oyster shell whiting, nanometer
Prepared by oyster shell whiting, prepared by complex microsphere, complex microsphere is modified, and specifically includes following steps：
It is prepared by thick oyster shell whiting：Shell is cleaned up, soaks 4-5h with dilute acid soln, then with sig water and wash, removal shellfish
Shell surface impurity, is finally cleaned with clear water, drying, then calcines 2-3h at 900-1000 DEG C, is cooled to room temperature, mistake after grinding
150-200 mesh sieves, up to thick oyster shell whiting, which make it that calcium carbonate is converted into calcium oxide in shell powder, reduces calcium carbonate
Content, increases the content of organic matter, and greatly increases the content of active function groups in oyster shell whiting, and calcining can make the carbon in oyster shell whiting
Sour calcium is changed into porous fibrous double helix construction structure, has outstanding adsorptivity, is conducive to adsorb more chitosans so that inhales
The effect of attached heavy metal is more preferable, it may have antibacterial, sterilizing ability；
It is prepared by nanometer oyster shell whiting：The grinding dispersion agent of thick oyster shell whiting weight 1.7-2.2% is added into thick oyster shell whiting, is then used
Nano grinder crushes, and up to nanometer oyster shell whiting, grinding dispersion agent is that weight ratio is 1:1.1-1.3:0.02-0.03's
The mixture of PEG2000, calgon and dextran, each component of grinding dispersion agent can play synergistic effect, make shellfish
The Zeta potential absolute value of shell powder increases, and is not easy to reunite between particle, it is easy to be diffused on oyster shell whiting particle surface, form
Firm coating layer, is effectively reduced the surface-active of particle, so that additional size reduction energy focuses more on the crushing of particle
On, reach more satisfied grinding dispersion state, improve crushing material efficiency and its water dispersible, the particle diameter of nanometer oyster shell whiting are
20-100nm, the nanometer oyster shell whiting of the fineness are easily dispersed when preparing complex microsphere, by increasing capacitance it is possible to increase and the contact surface of chitosan
Product so that more chitosans can be fixed on oyster shell whiting, and then improve the ability of complex microsphere absorption heavy metal；
It is prepared by complex microsphere：Chitosan powder and oyster shell whiting are mixed and are dissolved in 1.8-2.2wt% acetic acid aqueous solutions, be made into containing
The Chitosan powder of 3-5wt% and the mixed solution of oyster shell whiting, as dispersed phase, 96- is added to by 1.8-2.2wt% Si Pan 60
In 99wt% normal octane solution, continuous phase is used as after mixing, drop shaping, then carries out crosslinking in water-bath solidify liquid and change
Property, clean up, dry, up to complex microsphere, the addition of oyster shell whiting not only increases the mechanical stability of chitin carrier, but also
The complexing power of carrier and transition metal can be improved, changes the application amount of oyster shell whiting and crosslinking agent, it can be achieved that being carried to microballoon
The regulation and control of body comprehensive performance；
Complex microsphere is modified：8-10wt% complex microspheres are added to thiocarbamide containing 1.8-2.2wt% and 0.8-1.2wt% epoxy chloropropionates
In the acetone soln of alkane, stirring reaction 4-6h, cleans up at 50-70 DEG C, dry, up to complex microsphere product, the step
In using epoxychloropropane as initiator, the chlorine atom of the amino after substitution crosslinking in chitosan molecule, forms intermediate product, then will
For thiocarbamide as initiator, the ammonia atom of its amino may replace the chlorine atom on intermediate product so that the amino of modified microballoon
Quantity can reach three times of unmodified complex microsphere so that complex microsphere has higher adsorption capacity and faster absorption speed
Rate, greatly improves the ability of complex microsphere absorption heavy metal.
Preferably, drop is shaped to：Dispersed phase is passed through in micro-fluidic chip passage with single channel syringe pump, uses bilateral
Continuous phase is passed through the continuous phase entrance of micro-fluidic chip by road syringe pump, makes it in the cross aisle of micro-fluidic chip to scattered
Mutually sheared, be incorporated into after droplet shearing balling-up with the outlet of micro-fluidic chip in water-bath solidify liquid.Dispersed phase in the step
Be subject to shearing force effect and itself existing surface tension and cut has height for droplet one by one, prepared microballoon
Monodispersity, uniform particle sizes.
Preferably, water-bath solidify liquid uses 0.4-0.6wt% glutaraldehyde water solutions, 1.8-2.2wt% Si Pan 60 and normal octane
Solution mixed preparing forms.After the droplet sheared enters water-bath solidify liquid, glutaraldehyde can from water-bath solidify liquid from outer and
Interior is diffused into droplet, and as crosslinking agent, with the aldehyde radical of glutaraldehyde schiff bases can occur glutaraldehyde for the amino on chitosan
Reaction, tridimensional network is cross-linked into by the chain structure of chitosan molecule, and cross-linking reaction first occurs in outer surface, then including
Portion occurs, and after curing, is further shunk to microballoon by receiving the n-octyl alcohol in phase so that and particle becomes more consolidation, stablizes,
With elasticity.
Compared with prior art, the advantage of the invention is that：1）Complex microsphere of the present invention combines oyster shell whiting and chitosan
Advantage, the addition of oyster shell whiting not only increases the mechanical stability of chitin carrier, but also can improve carrier and transition metal
Complexing power, it can be achieved that the recycling of heavy metal；2）The complex microsphere has higher adsorption capacity and inhales faster
Attached speed, it is strong to adsorb the ability of heavy metal, and it is strong to repeat usability, still shown after 6 adsorption-desorption cycles are undergone compared with
Strong adsorption capacity, while there is antibiotic property；3）Preparation method combination drop of the present invention shaping and cross-linking modified so that preparation
Microballoon has high monodispersity, and microspherulite diameter size, pattern, particle diameter and component are controllable, uniform particle sizes, high mechanical strength；4）
Chitosan is fixed on oyster shell whiting by the preparation method, solves that chitosan physicochemical properties are unstable, are soluble in diluted acid, machine
The problems such as tool intensity is not high, easily molded, improves the performance of chitosan.
Embodiment
The present invention program is described further below by embodiment：
Embodiment 1：
A kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, Chitosan powder and the weight ratio of oyster shell whiting in complex microsphere
For 1:0.3-0.45, the diameter of complex microsphere is for 0.4-0.6mm.
A kind of preparation method for the oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, including prepared by thick oyster shell whiting, nanometer
Prepared by oyster shell whiting, prepared by complex microsphere, complex microsphere is modified, and specifically includes following steps：
1）It is prepared by thick oyster shell whiting：Shell is cleaned up, soaks 4-5h with dilute acid soln, then with sig water and wash, removal
Shell surface impurity, is finally cleaned with clear water, drying, then calcines 2-3h at 900-1000 DEG C, is cooled to room temperature, mistake after grinding
150-200 mesh sieves, up to thick oyster shell whiting；
2）It is prepared by nanometer oyster shell whiting：The grinding dispersion agent of thick oyster shell whiting weight 1.7-2.2% is added into thick oyster shell whiting, is then made
Crushed with nano grinder, up to the nanometer oyster shell whiting that particle diameter is 20-100nm, grinding dispersion agent is that weight ratio is 1:1.1-
1.3:The mixture of the PEG2000 of 0.02-0.03, calgon and dextran；
3）It is prepared by complex microsphere：Chitosan powder and oyster shell whiting are mixed and are dissolved in 1.8-2.2wt% acetic acid aqueous solutions, is made into and contains
There are the Chitosan powder of 3-5wt% and the mixed solution of oyster shell whiting, as dispersed phase, 1.8-2.2wt% Si Pan 60 is added to 96-
In 99wt% normal octane solution, continuous phase is used as after mixing, drop shaping, then carries out crosslinking in water-bath solidify liquid and change
Property, clean up, dry, up to complex microsphere；
4）Complex microsphere is modified：8-10wt% complex microspheres are added to thiocarbamide containing 1.8-2.2wt% and 0.8-1.2wt% epoxy chlorine
In the acetone soln of propane, stirring reaction 4-6h, cleans up at 50-70 DEG C, dry, up to complex microsphere product.
Drop is shaped in above-mentioned steps 3：Dispersed phase is passed through in micro-fluidic chip passage with single channel syringe pump, is used
Continuous phase is passed through the continuous phase entrance of micro-fluidic chip by binary channels syringe pump, makes it right in the cross aisle of micro-fluidic chip
Dispersed phase is sheared, and is incorporated into after droplet shearing balling-up with the outlet of micro-fluidic chip in water-bath solidify liquid.
Water-bath solidify liquid uses 0.4-0.6wt% glutaraldehyde water solutions in above-mentioned steps 3,1.8-2.2wt% Si Pan 60 and just
Octane solution mixed preparing forms.
Embodiment 2：
A kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, Chitosan powder and the weight ratio of oyster shell whiting in complex microsphere
For 1:0.45, the diameter of complex microsphere is for 0.4-0.6mm.
A kind of preparation method for the oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, specifically includes following steps：
1）It is prepared by thick oyster shell whiting：Shell is cleaned up, soaks 5h with dilute acid soln, then with sig water and wash, removal shellfish
Shell surface impurity, is finally cleaned with clear water, drying, then calcines 3h at 900 DEG C, is cooled to room temperature, and 150 mesh sieves are crossed after grinding,
Up to thick oyster shell whiting；
2）It is prepared by nanometer oyster shell whiting：The grinding dispersion agent of thick oyster shell whiting weight 2.2% is added into thick oyster shell whiting, then using receiving
Rice pulverizer crushes, and up to the nanometer oyster shell whiting that particle diameter is 20-100nm, grinding dispersion agent is that weight ratio is 1:1.3:0.02
The mixture of PEG2000, calgon and dextran；
3）It is prepared by complex microsphere：Chitosan powder and oyster shell whiting are mixed and are dissolved in 2.1wt% acetic acid aqueous solutions, be made into containing
The Chitosan powder of 5wt% and the mixed solution of oyster shell whiting, as dispersed phase, 96wt% normal octanes are added to by 1.8wt% Si Pan 60
In solution, it is used as continuous phase after mixing, then drop shaping carries out cross-linking modified in water-bath solidify liquid, clean up,
Drying, up to complex microsphere；
4）Complex microsphere is modified：10wt% complex microspheres are added to the acetone of thiocarbamide containing 1.8wt% and 1.2wt% epoxychloropropane
In solution, stirring reaction 6h, cleans up at 50 DEG C, dry, up to complex microsphere product.
Drop is shaped in above-mentioned steps 3：Dispersed phase is passed through in micro-fluidic chip passage with single channel syringe pump, is used
Continuous phase is passed through the continuous phase entrance of micro-fluidic chip by binary channels syringe pump, makes it right in the cross aisle of micro-fluidic chip
Dispersed phase is sheared, and is incorporated into after droplet shearing balling-up with the outlet of micro-fluidic chip in water-bath solidify liquid.
Water-bath solidify liquid uses 0.4wt% glutaraldehyde water solutions, 2.2wt% Si Pan 60 and normal octane solution in above-mentioned steps 3
Mixed preparing forms.
Embodiment 3：
A kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, Chitosan powder and the weight ratio of oyster shell whiting in complex microsphere
For 1:0.38, the diameter of complex microsphere is for 0.4-0.6mm.
A kind of preparation method for the oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, including prepared by thick oyster shell whiting, nanometer
Prepared by oyster shell whiting, prepared by complex microsphere, complex microsphere is modified, and specifically includes following steps：
1）It is prepared by thick oyster shell whiting：Shell is cleaned up, soaks 4.5h with dilute acid soln, then with sig water and wash, removal
Shell surface impurity, is finally cleaned with clear water, drying, then calcines 2.5h at 950 DEG C, is cooled to room temperature, and 180 mesh are crossed after grinding
Sieve, up to thick oyster shell whiting；
2）It is prepared by nanometer oyster shell whiting：The grinding dispersion agent of thick oyster shell whiting weight 2.0% is added into thick oyster shell whiting, then using receiving
Rice pulverizer crushes, and up to the nanometer oyster shell whiting that particle diameter is 20-100nm, grinding dispersion agent is that weight ratio is 1:1.2:0.025
The mixture of PEG2000, calgon and dextran；
3）It is prepared by complex microsphere：Chitosan powder and oyster shell whiting are mixed and are dissolved in 2.0wt% acetic acid aqueous solutions, be made into containing
The Chitosan powder of 4wt% and the mixed solution of oyster shell whiting, as dispersed phase, 98wt% normal octanes are added to by 2.0wt% Si Pan 60
In solution, it is used as continuous phase after mixing, then drop shaping carries out cross-linking modified in water-bath solidify liquid, clean up,
Drying, up to complex microsphere；
4）Complex microsphere is modified：The acetone that 9wt% complex microspheres are added to thiocarbamide containing 2.0wt% and 1.0wt% epoxychloropropane is molten
In liquid, stirring reaction 5h, cleans up at 60 DEG C, dry, up to complex microsphere product.
Drop is shaped in above-mentioned steps 3：Dispersed phase is passed through in micro-fluidic chip passage with single channel syringe pump, is used
Continuous phase is passed through the continuous phase entrance of micro-fluidic chip by binary channels syringe pump, makes it right in the cross aisle of micro-fluidic chip
Dispersed phase is sheared, and is incorporated into after droplet shearing balling-up with the outlet of micro-fluidic chip in water-bath solidify liquid.
Water-bath solidify liquid uses 0.5wt% glutaraldehyde water solutions, 2.0wt% Si Pan 60 and normal octane solution in above-mentioned steps 3
Mixed preparing forms.
Embodiment 4：
A kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, Chitosan powder and the weight ratio of oyster shell whiting in complex microsphere
For 1:0.38, the diameter of complex microsphere is for 0.4-0.6mm.
A kind of preparation method for the oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, including prepared by thick oyster shell whiting, nanometer
Prepared by oyster shell whiting, prepared by complex microsphere, complex microsphere is modified, and specifically includes following steps：
1）It is prepared by thick oyster shell whiting：Shell is cleaned up, soaks 4.5h with dilute acid soln, then with sig water and wash, removal
Shell surface impurity, is finally cleaned with clear water, drying, then calcines 2.5h at 950 DEG C, is cooled to room temperature, and 180 mesh are crossed after grinding
Sieve, up to thick oyster shell whiting；
2）It is prepared by nanometer oyster shell whiting：It is 100 by weight:0.38-0.52 adds ethyl tartrate into thick oyster shell whiting, stirring
1-2h, stirs 3-5h, filtration drying, then adds the grinding dispersion agent of thick oyster shell whiting weight 2.0%, then into dried powder
Crushed using nano grinder, up to the nanometer oyster shell whiting that particle diameter is 20-100nm, grinding dispersion agent is that weight ratio is 1:1.2:
The mixture of 0.025 PEG2000, calgon and dextran, L-TARTARIC ACID diethylester in above-mentioned ethyl tartrate
Weight ratio with D- ethyl tartrates is 100:1.32-1.36, ethyl tartrate add can with thick oyster shell whiting
Polymerisation occurs for active group, and more active groups are provided for oyster shell whiting, while can obtain new chiral material, carries significantly
The ability of the bacteriums such as high oyster shell whiting identification fungi, and then can quickly kill the bacterium in waste water, and D- ethyl tartrates plus
Enter to improve the stereoselectivity of reaction, increase the yield of chiral reactant；
3）It is prepared by complex microsphere：Chitosan powder and oyster shell whiting are mixed and are dissolved in 2.0wt% acetic acid aqueous solutions, be made into containing
The Chitosan powder of 4wt% and the mixed solution of oyster shell whiting, as dispersed phase, 98wt% normal octanes are added to by 2.0wt% Si Pan 60
In solution, it is used as continuous phase after mixing, then drop shaping carries out cross-linking modified in water-bath solidify liquid, clean up,
Drying, up to complex microsphere；
4）Complex microsphere is modified：The acetone that 9wt% complex microspheres are added to thiocarbamide containing 2.0wt% and 1.0wt% epoxychloropropane is molten
In liquid, stirring reaction 5h, cleans up at 60 DEG C, dry, up to complex microsphere product.
Drop is shaped in above-mentioned steps 3：Dispersed phase is passed through in micro-fluidic chip passage with single channel syringe pump, is used
Continuous phase is passed through the continuous phase entrance of micro-fluidic chip by binary channels syringe pump, makes it right in the cross aisle of micro-fluidic chip
Dispersed phase is sheared, and is incorporated into after droplet shearing balling-up with the outlet of micro-fluidic chip in water-bath solidify liquid.
Water-bath solidify liquid uses 0.5wt% glutaraldehyde water solutions, 2.0wt% Si Pan 60 and normal octane solution in above-mentioned steps 3
Mixed preparing forms.
Embodiment 5：
Adsorb heavy metal performance test：
Embodiment 2,3 product of embodiment are set to test group, the microballoon for adsorbing heavy metal is set to control group.
Three parts of 100ml electroplating wastewaters are taken, the pH of the electroplating wastewater is 3.4, its primary chemical composition is：CN-：20mg/L,
Cr6+：82mg/L, Cu2+：28mg/L, Zn2+：40mg/L, Ni2+：20mg/L, adjust pH to 7 ~ 7.5 after, be separately added into embodiment 2,
The microballoon of 3 product of embodiment and absorption heavy metal, after addition 20g/L, standing adsorption 24h filtering be used as prepare liquid, it is to be measured
Liquid measures CN in solution with atomic absorption spectrophotometer-、Cr6+、Cu2+、Zn2+And Ni2+Concentration, calculate the suction to heavy metal
It is attached.Obtained adsorption rate is as follows：
Embodiment 2：CN-Adsorption rate=99.89%, Cr6+Adsorption rate=99.91%, Cu2+Adsorption rate=98.54%, Zn2+Suction
Attached rate=99.94%, Ni2+Adsorption rate=99.72%.
Embodiment 3：CN-Adsorption rate=99.92%, Cr6+Adsorption rate=99.94%, Cu2+Adsorption rate=99.90%, Zn2+
Adsorption rate=99.97%, Ni2+Adsorption rate=99.78%.
Control group：CN-Adsorption rate=92.31%, Cr6+Adsorption rate=87.52%, Cu2+Adsorption rate=80.49%, Zn2+
Adsorption rate=93.45%, Ni2+Adsorption rate=90.68%.
From above-mentioned data, the heavy metal out of electroplating wastewater adsorption rate by 3 product treatment of embodiment 2 and embodiment is bright
It is aobvious to be better than reference examples, illustrate the advantages of good adsorption effect of embodiment 2 and 3 product of embodiment to effluent containing heavy metal ions.
Routine operation in the operating procedure of the present invention is well known to those skilled in the art, herein without repeating.
Technical scheme is described in detail in embodiment described above, it should be understood that the above is only
For the specific embodiment of the present invention, it is not intended to limit the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.
Claims (10)
- A kind of 1. oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, it is characterised in that：Chitosan powder in the complex microsphere The weight ratio of end and oyster shell whiting is 1:0.3-0.45.
- A kind of 2. oyster shell whiting chitosan compound microsphere for adsorbing heavy metal according to claim 1, it is characterised in that：It is described The diameter of complex microsphere is for 0.4-0.6mm.
- 3. a kind of preparation method for the oyster shell whiting chitosan compound microsphere for adsorbing heavy metal, including prepared by thick oyster shell whiting, Namibe Prepared by shell powder, prepared by complex microsphere, complex microsphere is modified, it is characterised in that：The nanometer oyster shell whiting preparation process is：To thick shellfish Grinding dispersion agent is added in shell powder, is then crushed using nano grinder, up to nanometer oyster shell whiting.
- 4. a kind of preparation method of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal according to claim 3, it is special Sign is：The additive amount of grinding dispersion agent is thick oyster shell whiting weight 1.7-2.2% in the nanometer oyster shell whiting preparation process, described Grinding dispersion agent is that weight ratio is 1:1.1-1.3:The mixing of the PEG2000 of 0.02-0.03, calgon and dextran Thing.
- 5. a kind of preparation method of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal according to claim 3, it is special Sign is：The particle diameter of the nanometer oyster shell whiting is 20-100nm.
- 6. a kind of preparation method of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal according to claim 3, it is special Sign is：The thick oyster shell whiting preparation process is：Shell is cleaned up, 4-5h is soaked with dilute acid soln, cleans, drying, then 2-3h is calcined at 900-1000 DEG C, is cooled to room temperature, 150-200 mesh sieves are crossed after grinding, up to thick oyster shell whiting.
- 7. a kind of preparation method of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal according to claim 3, it is special Sign is：The complex microsphere preparation process is：It is water-soluble that Chitosan powder and oyster shell whiting mixing are dissolved in 1.8-2.2wt% acetic acid In liquid, the mixed solution of the Chitosan powder containing 3-5wt% and oyster shell whiting is made into, as dispersed phase, by 1.8-2.2wt% Si Pan 60 are added in 96-99wt% normal octane solution, and continuous phase, drop shaping, then in water-bath solidify liquid are used as after mixing Carry out cross-linking modified, clean up, up to complex microsphere.
- 8. a kind of preparation method of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal according to claim 7, it is special Sign is：Drop is shaped in the complex microsphere preparation process：Dispersed phase is passed through micro-fluidic chip with single channel syringe pump In passage, continuous phase is passed through to the continuous phase entrance of micro-fluidic chip using binary channels syringe pump, makes it in micro-fluidic chip Dispersed phase is sheared in cross aisle, water-bath solidify liquid is introduced with the outlet of micro-fluidic chip after droplet shearing balling-up In.
- 9. a kind of preparation method of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal according to claim 7, it is special Sign is：Water-bath solidify liquid uses 0.4-0.6wt% glutaraldehyde water solutions, 1.8-2.2wt% in the complex microsphere preparation process This Pan 60 and normal octane solution mixed preparing form.
- 10. a kind of preparation method of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal according to claim 3, it is special Sign is：The complex microsphere modification procedure is：8-10wt% complex microspheres are added to thiocarbamide containing 1.8-2.2wt% and 0.8- In the acetone soln of 1.2wt% epoxychloropropane, stirring reaction 4-6h, cleans up at 50-70 DEG C, dry, up to compound micro- Ball product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711182044.0A CN107952416B (en) | 2017-11-23 | 2017-11-23 | Shell powder chitosan composite microsphere for adsorbing heavy metals and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711182044.0A CN107952416B (en) | 2017-11-23 | 2017-11-23 | Shell powder chitosan composite microsphere for adsorbing heavy metals and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107952416A true CN107952416A (en) | 2018-04-24 |
| CN107952416B CN107952416B (en) | 2021-04-23 |
Family
ID=61961667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711182044.0A Active CN107952416B (en) | 2017-11-23 | 2017-11-23 | Shell powder chitosan composite microsphere for adsorbing heavy metals and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107952416B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629401A (en) * | 2019-09-23 | 2019-12-31 | 晋江市达亿经编织造有限公司 | Antibacterial textile material and preparation method thereof |
| CN110721664A (en) * | 2019-10-10 | 2020-01-24 | 浙江海洋大学 | Preparation method of mussel shell powder/carboxymethyl cellulose composite gel adsorbent |
| CN110921813A (en) * | 2019-09-30 | 2020-03-27 | 浙江海洋大学 | Application of modified mussel shell filler in biological aerated filter for sewage treatment |
| CN111530436A (en) * | 2020-04-28 | 2020-08-14 | 中国科学院海洋研究所 | Method for modifying shells |
| CN111774039A (en) * | 2020-06-12 | 2020-10-16 | 中国热带农业科学院农产品加工研究所 | Preparation and use of recyclable carboxymethyl chitosan/shell powder composite material capable of adsorbing Cd/Pb |
| CN112978940A (en) * | 2021-04-22 | 2021-06-18 | 广州市点滴生物科技有限公司 | Organic sewage biological fermentation treating agent and preparation method thereof |
| CN113896310A (en) * | 2021-11-16 | 2022-01-07 | 温州大学 | Preparation and application method of shell powder modified organic polymeric flocculant |
| CN115433584A (en) * | 2022-08-17 | 2022-12-06 | 吉林建筑大学 | Calcium peroxide-sodium persulfate synergistic in-situ remediation method for organic composite polluted site |
| CN117551165A (en) * | 2024-01-12 | 2024-02-13 | 鲁东大学 | Preparation method of abalone viscera peptide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009014532A1 (en) * | 2007-07-20 | 2009-01-29 | Mylan Pharmaceuticals, Inc. | Stabilized tolterodine tartrate formulations |
| WO2012074468A1 (en) * | 2010-11-30 | 2012-06-07 | Ge Healthcare Bio-Sciences Ab | Buffering compositions enclosed in a size exclusion matrix |
| CN103585950A (en) * | 2013-12-02 | 2014-02-19 | 浙江海洋学院 | Preparation method of natural shell adsorbent |
| CN105617998A (en) * | 2015-12-29 | 2016-06-01 | 华东理工大学 | Preparing method for modified chitosan adsorbent |
| CN105879844A (en) * | 2016-05-26 | 2016-08-24 | 青岛科技大学 | Method for preparing composite shellfish toxin adsorbent by coating porous shell particles with chitosan |
| CN106238005A (en) * | 2016-10-08 | 2016-12-21 | 黎明职业大学 | A kind of chitosan Concha Ostreae complex microsphere and preparation method thereof |
-
2017
- 2017-11-23 CN CN201711182044.0A patent/CN107952416B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009014532A1 (en) * | 2007-07-20 | 2009-01-29 | Mylan Pharmaceuticals, Inc. | Stabilized tolterodine tartrate formulations |
| WO2012074468A1 (en) * | 2010-11-30 | 2012-06-07 | Ge Healthcare Bio-Sciences Ab | Buffering compositions enclosed in a size exclusion matrix |
| CN103585950A (en) * | 2013-12-02 | 2014-02-19 | 浙江海洋学院 | Preparation method of natural shell adsorbent |
| CN105617998A (en) * | 2015-12-29 | 2016-06-01 | 华东理工大学 | Preparing method for modified chitosan adsorbent |
| CN105879844A (en) * | 2016-05-26 | 2016-08-24 | 青岛科技大学 | Method for preparing composite shellfish toxin adsorbent by coating porous shell particles with chitosan |
| CN106238005A (en) * | 2016-10-08 | 2016-12-21 | 黎明职业大学 | A kind of chitosan Concha Ostreae complex microsphere and preparation method thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629401A (en) * | 2019-09-23 | 2019-12-31 | 晋江市达亿经编织造有限公司 | Antibacterial textile material and preparation method thereof |
| CN110629401B (en) * | 2019-09-23 | 2020-07-24 | 晋江市达亿经编织造有限公司 | Antibacterial textile material and preparation method thereof |
| CN110921813B (en) * | 2019-09-30 | 2021-11-09 | 浙江海洋大学 | Application of modified mussel shell filler in biological aerated filter for sewage treatment |
| CN110921813A (en) * | 2019-09-30 | 2020-03-27 | 浙江海洋大学 | Application of modified mussel shell filler in biological aerated filter for sewage treatment |
| CN110721664B (en) * | 2019-10-10 | 2021-12-17 | 浙江海洋大学 | Preparation method of mussel shell powder/carboxymethyl cellulose composite gel adsorbent |
| CN110721664A (en) * | 2019-10-10 | 2020-01-24 | 浙江海洋大学 | Preparation method of mussel shell powder/carboxymethyl cellulose composite gel adsorbent |
| CN111530436A (en) * | 2020-04-28 | 2020-08-14 | 中国科学院海洋研究所 | Method for modifying shells |
| CN111774039A (en) * | 2020-06-12 | 2020-10-16 | 中国热带农业科学院农产品加工研究所 | Preparation and use of recyclable carboxymethyl chitosan/shell powder composite material capable of adsorbing Cd/Pb |
| CN112978940A (en) * | 2021-04-22 | 2021-06-18 | 广州市点滴生物科技有限公司 | Organic sewage biological fermentation treating agent and preparation method thereof |
| CN112978940B (en) * | 2021-04-22 | 2021-07-16 | 广州市点滴生物科技有限公司 | Organic sewage biological fermentation treating agent and preparation method thereof |
| CN113896310A (en) * | 2021-11-16 | 2022-01-07 | 温州大学 | Preparation and application method of shell powder modified organic polymeric flocculant |
| CN115433584A (en) * | 2022-08-17 | 2022-12-06 | 吉林建筑大学 | Calcium peroxide-sodium persulfate synergistic in-situ remediation method for organic composite polluted site |
| CN115433584B (en) * | 2022-08-17 | 2024-04-19 | 吉林建筑大学 | Synergistic in-situ repair method for calcium peroxide-sodium persulfate in organic composite polluted site |
| CN117551165A (en) * | 2024-01-12 | 2024-02-13 | 鲁东大学 | Preparation method of abalone viscera peptide |
| CN117551165B (en) * | 2024-01-12 | 2024-03-19 | 鲁东大学 | Preparation method of abalone viscera peptide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107952416B (en) | 2021-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107952416A (en) | A kind of oyster shell whiting chitosan compound microsphere for adsorbing heavy metal and preparation method thereof | |
| Yadav et al. | Adsorptive potential of modified plant-based adsorbents for sequestration of dyes and heavy metals from wastewater-A review | |
| Xu et al. | Removal of anionic pollutants from liquids by biomass materials: a review | |
| Bhatnagar et al. | Applications of chitin-and chitosan-derivatives for the detoxification of water and wastewater—a short review | |
| CN102350324B (en) | Multifunctional composite adsorbent, and preparation method and application thereof | |
| CN101347719B (en) | Chitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent and preparation method thereof | |
| CN100453471C (en) | Preparation method for organic polymer-diatomaceous soil composite coagulating agent | |
| CN108439525A (en) | A kind of sewage-treating agent for heavy metal pollution | |
| CN102887581B (en) | Flocculating agent for treating sewage in Chinese patent medicine production enterprises and preparation method thereof | |
| Tatarchuk et al. | Green and ecofriendly materials for the remediation of inorganic and organic pollutants in water | |
| Calugaru et al. | Metals and metalloids treatment in contaminated neutral effluents using modified materials | |
| Deihimi et al. | Equilibrium and kinetic studies of ferricyanide adsorption from aqueous solution by activated red mud | |
| CN111085537B (en) | Method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials | |
| CN106076261A (en) | A kind of adsorbent for heavy metal and preparation method and application | |
| CN101274264B (en) | Preparation of composite adsorbing agent for effectively removing arsenic and method for using the same | |
| CN103301803A (en) | Preparation method of attapulgite-modified clay for ammonia-nitrogen wastewater treatment | |
| Nafi et al. | Removal of hazardous ions from aqueous solutions: Current methods, with a focus on green ion flotation | |
| CN111978595B (en) | Environment-friendly silver-loaded antibacterial agent based on plant waste powder and preparation method thereof | |
| CN109608021A (en) | Deep dehydration method for sludge | |
| Vasconcelos et al. | Competitive adsorption of Cu (II) and Cd (II) ions on spray-dried chitosan loaded with Reactive Orange 16 | |
| Ballester et al. | Design of remediation pilot plants for the treatment of industrial metal-bearing effluents (BIOMETAL DEMO project): Lab tests | |
| CN102078792A (en) | Synthesis method and application of nano-titanium dioxide for adsorption of heavy metals | |
| Gedam et al. | Blended composites of chitosan: adsorption profile for mitigation of toxic Pb (II) ions from water | |
| CN106630085A (en) | Environment-friendly treating agent for heavy metal-containing wastewater | |
| Shafique | Removal of toxic pollutants from aqueous medium through adsorption: a review |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |