CN101347719B - Chitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent and preparation method thereof - Google Patents
Chitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a chitosan/layered silicate nano composite porous crosslinked microsphere adsorbent and a preparation method thereof; in the adsorbent, the layered silicate which is in nano-state is dispersed in the chitosan microsphere which is treated with chemical crosslinking. The preparation method is as follows: the chitosan with low molecular weight/ layered silicate intercalation solution is prepared, the intercalation solution is blended with the chitosan with high molecular weight and is contacted with alkaline coagulant to prepare the microsphere, the microsphere is treated with pre-crosslinking and crosslinking, acid solution is used for removing pre-crosslinking agent to obtain the chitosan/layered silicate nano composite porous crosslinked microsphere adsorbent. By comprehensively utilizing the characters of chitosan and layered silicate in terms of adsorption property and jointly applying intercalation composition, solidification and granulation by alkali solution, and pre-crosslinking and crosslinking techniques, a porous microsphere adsorbent which has low price and excellent adsorption performance for heavy metal ions and organic pollutants can be prepared.
Description
Technical field
The present invention relates to a kind of technology of preparing of sorbent material, relate in particular to a kind of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent material and preparation method thereof.
Background technology
Contain overproof waste water such as heavy metal substance such as mercury, lead, cadmium, nickel, selenium, arsenic, chromium, thallium, bismuth, vanadium, gold, platinum, silver in the water and be called heavy metal containing sewage.Heavy metal containing sewage generally derives from mining and smelting process, trade waste, leather-making waste water, textile mills' waste water, electroplating wastewater and battery industry waste water, house refuse (as battery, cosmetics).Heavy metal containing sewage has direct physiology toxicity to people, animal; Irrigate the crops with the water that contains heavy metal, can make crop be subjected to heavy metal pollution, cause agricultural product toxic; Be deposited on river bed, bay, enter food chain, enter human body through aquatic products such as fish by water plant.
Contain the efficient processing of heavy metal containing sewage and be the important topic of domestic and international water treatment worker and material supplier author's research always the recycling of heavy metal.At present, the processing method of comparison system has chemical precipitation method, physico-chemical process and microbial method.Chemical precipitation method is as using wider a kind of method on the engineering, this method can be removed most of heavy metal substance, and method is simple, but the body refuse precipitation slowly, is difficult to purification of waste water to allow compliance with emission standards.In addition, because chemical method generally will add a large amount of chemical agents, and become sedimentary form and be precipitated out, this has just determined can have a large amount of secondary pollutions after the chemical Treatment, generation as a large amount of waste residues, and the processing of these waste residues still do not have at present and handles method of disposal preferably, so all there are huge negative effect in its application on engineering and later sustainable development.
The microbial method processing contains heavy metal containing sewage and has obtained remarkable progress in recent years, its Study on Theory is also deepened continuously, obtained applying to a certain degree, but remaining in significant problem aspect the recovery of heavy metal substance, in addition owing to the factor that influences microbial activity is very complicated, for the source of sewage condition
The adaptability of microorganism also has problems under the change situation.
Physico-chemical process is that new method is administered in the heavy metal pollution that development in recent years is got up.Physico-chemical process adopts methods such as ion-exchange, absorption, extraction, counter-infiltration except that the heavy metal in the decontaminated water.Prepared different kinds of ions exchanger resin and ion-exchange fibre, but because majority is artificial synthesized polymer material, had pollution problem in the preparation process, material itself is difficult to biodegradation in addition, does not therefore in fact fundamentally solve environmental problem.
Shitosan be natural chitin take off the acetyl product, be a kind of natural polysaecharides material that extensively is present in shellfish and insect shell.A large amount of free amino groups and hydroxyl activity group are arranged in its molecular structure, and free amino group wherein has and aliphatic primary amine chemical reaction characteristic much at one, has the function of chelating heavy metal ion.In slightly acidic water solution, have a large amount of-NH in the chitosan molecule structure
3+Group, and become polyelectrolyte class material.About the development and use extremely attention of every field always of shitosan and derivative thereof, particularly its unique adsorption function has obtained deep research especially.Shitosan is to various heavy metal ion, as: Co
2+, Ni
2+, Mn
2+, As
2+, Cr
2+Deng absorption property, to the aspects such as absorption of the small organic molecule matter in the waste water from dyestuff, a large amount of research reports is all arranged both at home and abroad.
Because shitosan can be dissolved in the weakly acidic solution, therefore as sorbing material, the recycling performance of shitosan is relatively poor, with shitosan carry out suitable crosslinked and make spherical particle can make recycle and water treatment procedure in the excessive problem of pressure obtain certain solution, but often the adsorption function of shitosan can be subjected to certain influence.
Layered silicate material is the inorganic mineral with layer structure, in China abundant deposit is arranged.Have structure channel in the crystal structure of phyllosilicate, with the macromolecular material recombination process in, interlamellar spacing is enlarged even strut fully.Because layered silicate material has bigger specific area and certain cation exchange capacity, thereby the good adsorption performance is arranged, and has selectivity, can be used to handle all kinds of sewage after the diverse ways modification.But owing to the laminar silicic acid salting liquid has colloidal nature, be dispersed in to have suitable stability in the water, therefore must use flocculant just can make its precipitation.In addition, to reclaim also be unusual difficulty for the desorption that is adsorbed in the heavy metal substance in the mud shape phyllosilicate.
Summary of the invention
Embodiment of the present invention provides a kind of preparation method of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, utilize phyllosilicate and the shitosan characteristics aspect absorption property, by the associating of kinds of processes, prepare and a kind of heavy metal ion and organic pollution are had efficient adsorbing separation ability and cheap porous microsphere sorbent.
The objective of the invention is to be achieved through the following technical solutions:
Embodiment of the present invention provides a kind of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, and this adsorbent is scattered in the chitosan microball of chemical crosslinking with the nanometer state by phyllosilicate.
Layered silicate is scattered in the crosslinked chitosan microball of formaldehyde precrosslink and epoxychloropropane with the intercalation or the state of peeling off.
Embodiment of the present invention provides a kind of preparation method of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, this method comprises: preparation low-molecular weight chitoglycan/phyllosilicate intercalation solution, with described intercalation solution mix with high molecular weight chitosan and with alkaline coagulating agent contact preparation microballoon, microballoon is carried out precrosslink and crosslinking Treatment, obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent after removing the precrosslink agent with acid solution again.
Described method further comprises:
(1) preparation phyllosilicate suspension: phyllosilicate 1～20 weight portion adds 100～500 weight parts waters, stirs 1～6 hour down at 50～95 ℃, obtains the suspension of phyllosilicate;
(2) preparation low-molecular weight chitoglycan solution: it is in the acid solution of 1～8% (volume ratio) that 1～20 weight portion low-molecular weight chitoglycan is dissolved in 100～500 weight portion concentration, regulates pH value to 3～6, obtains the shitosan acid solution;
(3) preparation shitosan/phyllosilicate intercalated compound: above laminar silicic acid salt suspensioning liquid is mixed with the shitosan acid solution, and stirring reaction is 2～10 hours under 40～80 ℃ of temperature, obtains shitosan/phyllosilicate intercalated compound solution;
(4) preparation microballoon: 1～200 weight portion high molecular weight chitosan is joined in the above complex solution, under 40～80 ℃ of temperature, stir dissolving fully in 1～6 hour, and be injected in the dropping funel at 5～50cm place, liquid level top, splash in the NaOH solution that concentration is 0.1～1mol/L with 20～120 droplets/minute speed, make the microballoon that diameter is 2～10mm, filter, the flushing of water logging bubble obtains shitosan/phyllosilicate intercalated compound microballoon to neutral;
(5) preparation precrosslink microballoon: above microballoon is scattered in 50～200ml deionized water, adds the precrosslink agent, the concussion reaction is 1～10 hour under 20～80 ℃ of temperature, obtains the precrosslink microballoon;
(6) preparation stephanoporate crosslinked microsphere: pH value to 8～11 of regulating the precrosslink microspheres solution, and keep constant, add crosslinking agent, under 50～90 ℃ of temperature, stirred 1～6 hour, filter, be washed to be scattered in the acid solution after the neutrality and flood, remove the precrosslink agent, obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent after the freeze drying.
Described method further comprises:
(1) preparation phyllosilicate suspension: phyllosilicate 1～20 weight portion adds 100～500 weight parts waters, stirs 1～6 hour under 50～95 ℃ of temperature, obtains the suspension of phyllosilicate;
(2) preparation chitosan solution: it is in 1～8% the acetum that 1～20 weight portion low-molecular weight chitoglycan is dissolved in 100～500 weight portion concentration, regulates pH value to 3～6, obtains chitosan-acetic acid solution;
(3) preparation shitosan/phyllosilicate intercalated compound solution: above laminar silicic acid salt suspensioning liquid is mixed with chitosan-acetic acid solution, and stirring reaction is 2～10 hours under 40～80 ℃ of temperature, obtains shitosan/phyllosilicate intercalated compound solution;
(4) preparation shitosan/phyllosilicate intercalated compound microballoon: 1～200 weight portion high molecular weight chitosan is joined in the above complex solution, under 40～80 ℃ of temperature, stir dissolving fully in 1～6 hour, and be injected in the dropping funel at 5～50cm place, liquid level top, be added drop-wise in the NaOH solution that concentration is 0.1～1mol/L with 20～120 droplets/minute speed, make the microballoon that diameter is 2～10mm, filter, the flushing of water logging bubble obtains shitosan/phyllosilicate intercalated compound microballoon to neutral;
(5) preparation precrosslink shitosan/phyllosilicate intercalated compound microballoon: above microballoon is scattered in 50～200ml deionized water, adding is the formalin of 2:1～8:1 with the ratio of chitosan structure unit amount of substance, the concussion reaction is 1～10 hour under 20～80 ℃ of temperature, obtains the precrosslink microballoon;
(6) prepare cross linked porous shitosan/phyllosilicate intercalated compound microballoon: pH value to 8～11 of regulating the precrosslink microspheres solution, and keep constant, adding is the epoxychloropropane of 2:1～6:1 with the ratio of chitosan structure unit amount of substance, under 50～90 ℃ of temperature, stirred 1～6 hour, filter, be washed to be scattered in the acid solution after the neutrality and flood, remove the precrosslink agent, obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent after the freeze drying.
Layered silicate is any in imvite, kaolin, attapulgite, mica, atlapulgite, vermiculite, the diatomite.
Layered silicate cation exchange capacity is 5～120meq/100g.
Layered silicate particle diameter is 5～100 microns.
The content of described microballoon inner lamination silicate is 8～35wt%, and the preferred content of microballoon inner lamination silicate is 15～25wt%.
Described low-molecular weight chitoglycan viscosity average molecular weigh is 500～70000, and the preferred molecular weight of low-molecular weight chitoglycan is 10000～50000, and the more preferably molecular weight of low-molecular weight chitoglycan is 20000～45000.
Described high molecular weight chitosan molecular weight is 100,000～1,000,000, and the preferred molecular weight of high molecular weight chitosan is 300,000～900,000, and the more preferably molecular weight of high molecular weight chitosan is 500,000～800,000.
The deacetylation of described shitosan is 75%～100%, and the deacetylation of the preferred shitosan that uses is 80～100%, and more preferably the deacetylation of the shitosan of Shi Yonging is 90～100%, and most preferably the deacetylation of the shitosan of Shi Yonging is 95～100%.
The technical scheme that is provided by the invention described above embodiment as can be seen, embodiment of the present invention is by comprehensive utilization phyllosilicate and the characteristics of shitosan aspect absorption property, compound by intercalation, alkali lye solidifies balling-up, the use in conjunction of precrosslink and crosslinking process, under the prerequisite that does not influence the phyllosilicate absorption property, be made into microspheroidal, enlarged the range of application of laminar silicic acid salt adsorbent, improve adsorption process and removal process, increase work efficiency, prepare a kind of heavy metal ion and organic pollution absorption property excellence, and cheap porous microsphere sorbent.
Description of drawings
Fig. 1 be in the embodiment of the invention imvite (curve a), the X ray diffracting spectrum of shitosan (curve b) and shitosan/montmorillonite-based nano compound stephanoporate crosslinked microsphere (curve c);
Fig. 2 is the stereoscan photograph on the shitosan/montmorillonite-based nano complex microsphere surface of the embodiment of the invention;
Fig. 3 is the Adsorption of Cu of the embodiment of the invention
2+After the stereoscan photograph on shitosan/montmorillonite-based nano complex microsphere surface.
The specific embodiment
Embodiment of the present invention provides a kind of preparation method of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, by fully utilizing phyllosilicate and shitosan in the characteristics aspect the absorption property, compound by intercalation, alkali lye solidifies balling-up, the use in conjunction of precrosslink and crosslinking process, prepare and a kind of heavy metal ion and organic pollution are had efficient adsorbing separation ability and cheap porous microsphere sorbent, this adsorbent is to be scattered in the crosslinked chitosan microball of formaldehyde precrosslink and epoxychloropropane with the intercalation or the state of peeling off by phyllosilicate, this adsorbent is the preparation method specifically may further comprise the steps: prepare low-molecular weight chitoglycan/phyllosilicate intercalation solution earlier, mix with high molecular weight chitosan again and with alkaline coagulating agent contact preparation microballoon, microballoon is carried out precrosslink and crosslinking Treatment, obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent after removing the precrosslink agent with acid solution again.
For ease of understanding, content of the present invention is further elaborated below by specific embodiment.
Embodiment one
Present embodiment provides a kind of heavy metal ion and organic pollution is had the preparation method of efficient adsorbing separation ability and cheap porous microsphere sorbent, specifically comprises the steps:
(1) preparation phyllosilicate suspension: phyllosilicate 1～20 weight portion adds 100～500 weight parts waters, stirs 1～6 hour under 50～95 ℃ of temperature, obtains the suspension of phyllosilicate;
(2) preparation low-molecular weight chitoglycan solution: it is in the acid solution of 1～8% (volume ratio) that 1～20 weight portion low-molecular weight chitoglycan is dissolved in 100～500 weight portion concentration, regulates pH value to 3～6, obtains the shitosan acid solution;
(3) preparation shitosan/phyllosilicate intercalated compound: the described shitosan acid solution that makes in the layered silicate suspension that makes in above-mentioned (1) and above-mentioned (2) is mixed, stirring reaction is 2～10 hours under 40～80 ℃ of temperature, obtains shitosan/phyllosilicate intercalated compound solution;
(4) preparation microballoon: the high molecular weight chitosan of 1～200 weight portion is joined in the described complex solution that makes in above-mentioned (3), under 40～80 ℃ of temperature, stir dissolving fully in 1～6 hour, and be injected in the dropping funel at 5～50cm place, liquid level top, splash in the NaOH solution that concentration is 0.1～1mol/L with 20～120 droplets/minute speed, make the microballoon that diameter is 2～10mm, filter, the flushing of water logging bubble obtains shitosan/phyllosilicate intercalated compound microballoon to neutral;
(5) preparation precrosslink microballoon: the described compound microballoon that makes in above-mentioned (4) is scattered in 50～200ml deionized water, adds the precrosslink agent, the concussion reaction is 1～10 hour under 20～80 ℃ of temperature, obtains the precrosslink microballoon;
(6) preparation stephanoporate crosslinked microsphere: the pH value of the precrosslink microspheres solution that contains the precrosslink microballoon in above-mentioned (5) is adjusted to 8～11, and keep constant, add crosslinking agent, under 50～90 ℃ of temperature, stirred 1～6 hour, filter, be washed to be scattered in the acid solution after the neutrality and flood, remove the precrosslink agent, after the freeze drying, promptly obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent.
Based on the above method, present embodiment also provides a kind of method for preparing adsorbent of further optimization, specifically comprises the steps:
(1) preparation phyllosilicate suspension: phyllosilicate 1～20 weight portion adds 100～500 weight parts waters, stirs 1～6 hour under 50～95 ℃ of temperature, obtains the suspension of phyllosilicate;
(2) preparation chitosan solution: it is in 1～8% the acetum that 1～20 weight portion low-molecular weight chitoglycan is dissolved in 100～500 weight portion concentration, regulates pH value to 3～6, obtains chitosan-acetic acid solution;
(3) preparation shitosan/phyllosilicate intercalated compound solution: the described chitosan-acetic acid solution that makes in the layered silicate suspension that makes in above-mentioned (1) and above-mentioned (2) is mixed, stirring reaction is 2～10 hours under 40～80 ℃ of temperature, obtains shitosan/phyllosilicate intercalated compound solution;
(4) preparation shitosan/phyllosilicate intercalated compound microballoon: 1～200 weight portion high molecular weight chitosan is joined in the described complex solution that makes in above-mentioned (3), under 40～80 ℃ of temperature, stir dissolving fully in 1～6 hour, and be injected in the dropping funel at 5～50cm place, liquid level top, be added drop-wise in the NaOH solution that concentration is 0.1～1mol/L with 20～120 droplets/minute speed, make the microballoon that diameter is 2～10mm, filter, the flushing of water logging bubble obtains shitosan/phyllosilicate intercalated compound microballoon to neutral;
(5) preparation precrosslink shitosan/phyllosilicate intercalated compound microballoon: above microballoon is scattered in 50～200ml deionized water, adding is the formalin of 2:1～8:1 with the ratio of chitosan structure unit amount of substance, the concussion reaction is 1～10 hour under 20～80 ℃ of temperature, obtains the precrosslink microballoon;
(6) prepare cross linked porous shitosan/phyllosilicate intercalated compound microballoon: the pH value that contains the precrosslink microspheres solution of precrosslink microballoon in above-mentioned (5) is adjusted to 8～11, and keep constant, adding is the epoxychloropropane of 2:1～6:1 with the ratio of chitosan structure unit amount of substance, under 50～90 ℃ of temperature, stirred 1～6 hour, filter, be washed to be scattered in the acid solution after the neutrality and flood, remove the precrosslink agent, after the freeze drying, promptly obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent.
But any in said method in used phyllosilicate adopting montmorillonite, kaolin, attapulgite, mica, atlapulgite, vermiculite or the diatomite, the cationic exchange capacity of described phyllosilicate is 5～120meq/100g, particle diameter is 5～100 microns, the content of phyllosilicate is 8～35wt%, and the content of the phyllosilicate of optimizing in the reality is 15～25wt%.
The low-molecular weight chitoglycan viscosity average molecular weigh that is adopted in the said method is 500～70000, and the molecular weight of optimization is 10000～50000, and more the molecular weight of You Huaing is 20000～45000; The high molecular weight chitosan molecular weight that is adopted is 100,000～1,000,000, and the molecular weight of optimization is 300,000～900,000, and more the molecular weight of You Huaing is 500,000～800,000.
In above-mentioned preparation method, the deacetylation of the shitosan that is adopted is 75～100%, the deacetylation of preferred shitosan is 80～100%, and the deacetylation of preferred shitosan is 90～100%, and the deacetylation of most preferred shitosan is 95～100%.
Product shitosan/the sheet silicate nano compound stephanoporate crosslinked microsphere sorbent of embodiment of the invention preparation is used in the separation of solution heavy metal ion and organic pollution, concrete using method is: it is in the single of 10～100mmol/L or mixture-metal salting liquid or heavy metal and the organic mixed solution that shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere is scattered in 50～200ml concentration, and vibration is adsorbed to and reaches balance under 25～60 ℃ of temperature.Its absorbance variation is measured in heavy metal ion and organic characteristic absorption wavelength place respectively with ultraviolet-uisible spectrophotometer in the dilution back, calculates its concentration C, can calculate the adsorption capacity of this adsorbent easily according to following formula.
Q＝(C
0-C)V/W
In the formula, Q is equilibrium adsorption capacity (mmol/g); C
0Be respectively original solution and balance solution weight metal concentration (mmol/L) with C; V is liquor capacity (L), and W is adsorbent dry weight (g).
Preparation method by the embodiment of the invention and application experiment process are as can be known, shitosan exists with the cationic polyelectrolyte state in acid solution, can realize exchange with the phyllosilicate interlayer cation, thereby insert the sheet interlayer of silicate, the lamella of silicate is strutted, and be dispersed in the chitosan solution with the nanometer state, form shitosan/phyllosilicate intercalated compound solution.Shitosan in the intercalated compound solution and phyllosilicate sheet interlayer exist stronger static and Van der Waals force effect, on the chitosan molecule surfaces externally and internally that is adsorbed on the silicate lamella in various degree, after this solution chance alkali solidifies balling-up, phyllosilicate can effectively be wrapped in the microballoon, by precrosslink and crosslinking Treatment, can keep improving again under the prerequisite of shitosan absorption property the acid resistance and the mechanical strength of shitosan shortly preferably to microballoon.Proved that complex microsphere belongs to the polymolecular layer adsorption mechanism to heavy metal ion and organic absorption, be different from the monolayer adsorption mechanism of shitosan or phyllosilicate, the two is nano combined to have synergistic function to adsorption function.
Embodiment two
Present embodiment provides a kind of preparation method of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, specifically comprises the steps:
(1) in the deionized water of 150ml, adds imvite 5g, under 50 ℃ temperature, stirred 6 hours, obtain montmorillonite suspension liquid;
(2) use with described montmorillonite suspension liquid equal volume, molecular weight be 2.7 ten thousand, deacetylation is 94.2%, concentration is that the chitosan-acetic acid solution of 3% (wt%) mixes with this montmorillonite suspension liquid, the pH value of regulating mixed solution is 3.8; Stir process is 8 hours under 40 ℃ temperature, obtains shitosan/montmorillonite intercalation complex solution;
(3) taking by weighing the 4.8g molecular weight is 710,000, deacetylation is that 92.3 shitosan is dissolved in the complex solution in above-mentioned (2), after stirring 5 hours under 50 ℃ of temperature, be cooled to room temperature and inject dropping funel, regulating the funnel end is 22cm with the below liquid level, splashes into 20 droplets/minute speed in the NaOH solution of 0.3mol/L, slowly balling-up under the stirring condition, filter, the flushing that is soaked in water is to neutral;
(4) microballoon that obtains in above-mentioned (3) is scattered in the 100ml deionized water, adding 24.7ml concentration is 37% formalin, adjust the temperature to 40 ℃ of reactions 1 hour in the 200rmp/min constant temperature oscillator, the stage is warmed up to 80 ℃, 10 ℃ of reactions of every intensification 1 hour;
(5) transfer system pH to 10 with 2.0mol/L NaOH solution, add 11.8ml epoxychloropropane solution, be warmed up to 60 ℃, and be 11, reacted 5 hours with 2.0mol/L NaOH solution maintenance system pH;
(6) cool off, be washed to neutrality, be transferred in the 250mL flask, add the sulfuric acid of 150ml1mol/L, under vibration and 70 ℃ of temperature conditions, handled 9 hours, be washed to neutral postlyophilization, promptly obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent.
Embodiment three
Present embodiment provides a kind of preparation method of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, is specifically undertaken by following step:
(1) in the deionized water of 125ml, adds kaolin 4g, under 60 ℃ of temperature, stirred 5 hours, obtain Kaolin clay suspension;
(2) use with the molecular weight of described Kaolin clay suspension equal volume be 2.7 ten thousand, deacetylation is 95.2%, concentration is that the chitosan-acetic acid solution of 2% (wt%) mixes with this Kaolin clay suspension, regulating the pH value is 4.8, stir process is 6 hours under 50 ℃ of temperature, obtains shitosan/kaolin intercalation complex solution;
(3) take by weighing 3.8g, molecular weight is 650,000, deacetylation is that 91.3 shitosan is dissolved in the described complex solution that makes in above-mentioned (2), after stirring 4 hours under 60 ℃ of temperature, be cooled to room temperature and inject dropping funel, regulating the funnel end is 18cm with the below liquid level, splashes into 30 droplets/minute speed in the NaOH solution of 0.4mol/L, slowly balling-up under the stirring condition, filter, the flushing that is soaked in water is to neutral;
(4) above-mentioned (3) being washed to neutral microballoon is scattered in the deionized water of 120ml, adding 21.6ml, concentration are 37% formalin, adjust the temperature to 40 ℃ of reactions 1 hour in the 200rmp/min constant temperature oscillator, the stage is warming up to 70 ℃, 10 ℃ of reactions of every intensification 1 hour;
(5) transfer system pH to 9 with 2.0mol/L NaOH solution, add 10.6ml epoxychloropropane solution, be warming up to 70 ℃, and be 9, reacted 4 hours with 2.0mol/L NaOH solution maintenance system pH;
(6) cool off, be washed to neutrality, be transferred in the 250mL flask, add 150ml1mol/L sulfuric acid, under vibration and 70 ℃ of temperature conditions, handled 9 hours, be washed to neutral postlyophilization, promptly obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent.
Embodiment four
Present embodiment provides a kind of preparation method of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, specifically comprises the steps:
(1) in the deionized water of 100ml, adds attapulgite 3g, under 50 ℃ of temperature, stirred 6 hours, obtain attapulgite suspension;
(2) use with above-mentioned (1) in the molecular weight of the described attapulgite suspension equal volume that makes be 5.2 ten thousand, deacetylation is 91.3%, concentration is that the chitosan-acetic acid solution of 2% (wt%) mixes with this attapulgite suspension, regulate pH=4.8,60 ℃ of following stir process 7 hours, shitosan/attapulgite intercalated compound solution;
(3) taking by weighing the 2.8g molecular weight is 810,000, deacetylation is that 90.3 shitosan is dissolved in the above-mentioned intercalated compound solution, after stirring 6 hours under 50 ℃, be cooled to room temperature and inject dropping funel, regulating the funnel end is 25cm with the below liquid level, splashes into 20 droplets/minute speed in the NaOH solution of 0.35mol/L, slowly balling-up under the stirring condition, filter, be soaked in water and wash to neutrality;
(4) be scattered in the 150ml deionized water, adding 20.6ml, concentration are 37% formalin, adjust the temperature to 40 ℃ of reactions one hour in the 200rmp/min constant temperature oscillator, and the stage is warmed up to 70 ℃, and 10 ℃ every liter were reacted 1 hour;
(5) transfer system pH to 10 with 2.0mol/L NaOH solution, add 9.7ml epoxychloropropane solution, be warmed up to 60 ℃, and be 10, reacted 4 hours with 2.0mol/L NaOH solution maintenance system pH;
(6) cool off, be washed to neutrality, be transferred in the 250mL flask, add 150ml1mol/L sulfuric acid, under vibration and 70 ℃ of conditions, handle 9h, be washed to neutral postlyophilization, obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent.
Embodiment five
Present embodiment provides a kind of preparation method of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, specifically comprises the steps:
(1) add diatomite 2g in the 150ml deionized water, 50 ℃ were stirred 6 hours down, get diatomite suspension;
(2) with the molecular weight of equal volume be 4.1 ten thousand, deacetylation is 93.2%, concentration is that the chitosan-acetic acid solution of 3% (wt%) mixes with above-mentioned diatomite suspension, regulate pH=4.1,60 ℃ of following stir process 4 hours, obtain shitosan/diatomite intercalation complex solution;
(3) take by weighing 1.8g, molecular weight is 880,000, deacetylation is that 94.3 shitosan is dissolved in the above-mentioned complex solution that makes, after stirring 3 hours under 60 ℃ of temperature, be cooled to room temperature and inject dropping funel, regulating the funnel end is 20cm with the below liquid level, splashes into 30 droplets/minute speed in the NaOH solution of 0.4mol/L, slowly balling-up under the stirring condition, filter, the flushing that is soaked in water is to neutral;
(4) microballoon that is washed in above-mentioned (3) after the neutrality is scattered in the deionized water of 100ml, adding 19.7ml, concentration are 37% formalin, adjust the temperature to 40 ℃ of reactions 1 hour in the 200rmp/min constant temperature oscillator, the stage is warming up to 80 ℃, 10 ℃ of reactions of every intensification 1 hour;
(5) transfer system pH to 9 with 2.0mol/L NaOH solution, add 8.9ml epoxychloropropane solution, be warming up to 50 ℃, and be 9, reacted 6 hours with 2.0mol/L NaOH solution maintenance system pH;
(6) cool off, be washed to neutrality, be transferred in the 250mL flask, add 150ml1mol/L sulfuric acid, under vibration and 70 ℃ of temperature conditions, handled 9 hours, be washed to neutral postlyophilization, promptly obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent.
Embodiment six
Present embodiment provides a kind of preparation method of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent, specifically comprises the steps:
A, add imvite 2.5g in the 125ml deionized water, 60 ℃ were stirred 4 hours down, montmorillonite suspension liquid;
B, with the molecular weight of equal volume be 4.1 ten thousand, deacetylation is 92.1%, concentration is that the chitosan-acetic acid solution of 2% (wt%) mixes with above-mentioned montmorillonite suspension liquid, regulate pH=4.6,40 ℃ of following stir process 8 hours, shitosan/montmorillonite intercalation complex solution
C, to take by weighing the 1g molecular weight be 620,000, deacetylation is that 93.2 shitosan is dissolved in the above-mentioned intercalated compound solution, after stirring 4 hours under 40 ℃, be cooled to room temperature and inject dropping funel, regulating the funnel end is 20cm with the below liquid level, splashes into 20 droplets/minute speed in the NaOH solution of 0.4mol/L, slowly balling-up under the stirring condition, filter, be soaked in water and wash to neutrality
D, be scattered in the 80ml deionized water, add 16.4ml37% formalin, adjust the temperature to 40 ℃ of reactions one hour in the 200rmp/min constant temperature oscillator, the stage is warmed up to 60 ℃, 10 ℃ every liter reactions 1 hour,
E, transfer system pH to 9, add 7.9ml epoxychloropropane solution, be warmed up to 70 ℃, and be 9, reacted 3 hours with 2.0mol/L NaOH solution maintenance system pH with 2.0mol/L NaOH solution,
F, cooling are washed to neutrality, are transferred in the 250mL flask, add 150ml1mol/L sulfuric acid, handle 9h under vibration and 70 ℃ of conditions, be washed to neutral postlyophilization after, promptly obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent.
Phyllosilicate used in the foregoing description is an example with imvite, kaolin, attapulgite and diatomite only, and phyllosilicate also can adopt in mica, atlapulgite or the vermiculite etc. any.
Below experiment and the experimental result by various composite crosslinked microspheres are separated heavy metal ion in the solution is described further the embodiment of the invention.
(1) the experiment preparation of shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere
Adopt the shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent for preparing among the foregoing description two～embodiment six;
(2) shitosan/phyllosilicate nano complex microsphere X-ray diffraction analysis
Select shitosan/montmorillonite-based nano complex microsphere to carry out the X-ray diffraction analysis of crystalline texture as sample.Compare with pure imvite and shitosan, in the nano combined system, the sheet interlayer spacing of imvite obviously increases, and the crystallization degree of shitosan significantly lowers, and sees Fig. 1.The increase of cheating engaging layer spacing shows in the compound system has the part chitosan molecule to be inserted in the montmorillonite layer, and imvite can be scattered in the chitosan basal body resin with the nanometer state.The decline of shitosan crystallization degree is because the constraint effect that imvite is moved to the interlayer chitosan molecule on the one hand, cause the shitosan crystallizing power to descend, be because precrosslink and cross-linking reaction have been destroyed the crystalline texture of shitosan on the other hand, crystallization degree is descended.The shitosan crystallization degree reduces, and the molecules align regularity descends, and helps the absorption of metal ion and organic molecule.
(3) shitosan/phyllosilicate nano complex microsphere is to the adsorption capacity of heavy metal ion
With shitosan/montmorillonite-based nano complex microsphere is example, is 16.7% o'clock at imvite content, and having measured its equilibrium adsorption capacity to copper ion in the solution is 2.36mmol/g, and the pure chitosan crosslinked microsphere is 0.89mmol/g, and the pure silicon hydrochlorate is 0.52mmol/g.As seen the nano hybridization of shitosan and phyllosilicate obviously has synergistic function to the absorption of heavy metal ion, sees Fig. 2, Fig. 3.
As seen has the good adsorption separation function by the prepared ABSORBENTS ABSORPTION metal ion of preparation method in the embodiment of the invention.
In sum, pass through comprehensive utilization phyllosilicate and the characteristics of shitosan aspect absorption property in the embodiment of the invention, the use in conjunction compound by intercalation, that alkali lye solidifies balling-up, precrosslink and crosslinking process prepares heavy metal ion and organic pollution absorption property excellence and cheap porous microsphere sorbent.
The above; only be the preferable specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; protection domain of the present invention is not caused any restriction because of the relation of the succession between each embodiment yet; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (7)
1. the preparation method of a shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent is characterized in that, this method comprises:
(1) preparation phyllosilicate suspension: phyllosilicate 1～20 weight portion adds 100～500 weight parts waters, stirs 1～6 hour down at 50～95 ℃, obtains the suspension of phyllosilicate;
(2) preparation low-molecular weight chitoglycan solution: it is in 1～8% the acid solution, to regulate pH value to 3～6 by volume that 1～20 weight portion low-molecular weight chitoglycan is dissolved in 100～500 weight portion concentration, obtains the shitosan acid solution;
(3) preparation shitosan/phyllosilicate intercalated compound solution: above laminar silicic acid salt suspensioning liquid is mixed with the shitosan acid solution, and stirring reaction is 2～10 hours under 40～80 ℃ of temperature, obtains shitosan/phyllosilicate intercalated compound solution;
(4) preparation microballoon: 1～200 weight portion high molecular weight chitosan is joined in the above intercalated compound solution, under 40～80 ℃ of temperature, stir dissolving fully in 1～6 hour, and be injected in the dropping funel at 5～50cm place, liquid level top, splash in the NaOH solution that concentration is 0.1～1mol/L with 20～120 droplets/minute speed, make the microballoon that diameter is 2～10mm, filter, the flushing of water logging bubble obtains shitosan/phyllosilicate intercalated compound microballoon to neutral;
(5) preparation precrosslink microballoon: above microballoon is scattered in 50～200ml deionized water, adds the precrosslink agent, the concussion reaction is 1～10 hour under 20～80 ℃ of temperature, obtains the precrosslink microballoon;
(6) preparation stephanoporate crosslinked microsphere: pH value to 8～11 of regulating the precrosslink microspheres solution, and keep constant, add crosslinking agent, under 50～90 ℃ of temperature, stirred 1～6 hour, filter, be washed to be scattered in the acid solution after the neutrality and flood, remove the precrosslink agent, obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent after the freeze drying;
Wherein, the viscosity average molecular weigh of described low-molecular weight chitoglycan is 500～70000; Described high molecular weight chitosan molecular weight is 100,000～1,000,000.
2. method according to claim 1 is characterized in that, described method further comprises:
(1) preparation phyllosilicate suspension: phyllosilicate 1～20 weight portion adds 100～500 weight parts waters, stirs 1～6 hour under 50～95 ℃ of temperature, obtains the suspension of phyllosilicate;
(2) preparation chitosan solution: it is in 1～8% the acetum that 1～20 weight portion low-molecular weight chitoglycan is dissolved in 100～500 weight portion concentration, regulates pH value to 3～6, obtains chitosan-acetic acid solution;
(3) preparation shitosan/phyllosilicate intercalated compound solution: above laminar silicic acid salt suspensioning liquid is mixed with chitosan-acetic acid solution, and stirring reaction is 2～10 hours under 40～80 ℃ of temperature, obtains shitosan/phyllosilicate intercalated compound solution;
(4) preparation shitosan/phyllosilicate intercalated compound microballoon: 1～200 weight portion high molecular weight chitosan is joined in the above complex solution, under 40～80 ℃ of temperature, stir dissolving fully in 1～6 hour, and be injected in the dropping funel at 5～50cm place, liquid level top, be added drop-wise in the NaOH solution that concentration is 0.1～1mol/L with 20～120 droplets/minute speed, make the microballoon that diameter is 2～10mm, filter, the flushing of water logging bubble obtains shitosan/phyllosilicate intercalated compound microballoon to neutral;
(5) preparation precrosslink shitosan/phyllosilicate intercalated compound microballoon: above microballoon is scattered in 50～200ml deionized water, the ratio of adding and chitosan structure unit amount of substance is 2: 1～8: 1 a formalin, the concussion reaction is 1～10 hour under 20～80 ℃ of temperature, obtains the precrosslink microballoon;
(6) prepare cross linked porous shitosan/phyllosilicate intercalated compound microballoon: pH value to 8～11 of regulating the precrosslink microspheres solution, and keep constant, the ratio of adding and chitosan structure unit amount of substance is 2: 1～6: 1 a epoxychloropropane, under 50～90 ℃ of temperature, stirred 1～6 hour, filter, be washed to be scattered in the acid solution after the neutrality and flood, remove the precrosslink agent, obtain shitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent after the freeze drying.
3. method according to claim 1 and 2 is characterized in that, layered silicate is any in imvite, kaolin, attapulgite, mica, atlapulgite, vermiculite, the diatomite.
4. method according to claim 3 is characterized in that, layered silicate cation exchange capacity is 5～120meq/100g.
5. method according to claim 3 is characterized in that, layered silicate particle diameter is 5～100 microns.
6. method according to claim 1 and 2 is characterized in that, the molecular weight of described high molecular weight chitosan is 300,000～900,000.
7. method according to claim 1 and 2 is characterized in that, the molecular weight of described high molecular weight chitosan is 500,000～800,000.
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