CN103864193A - Preparation method of starch zeolite molecular sieve flocculating agent - Google Patents
Preparation method of starch zeolite molecular sieve flocculating agent Download PDFInfo
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Abstract
The invention discloses a preparation method of a starch zeolite molecular sieve flocculating agent. The preparation method comprises the steps of (1) adding distilled water into 2.0-10.0g of cassava starch, heating until boiling, and centrifuging at the rotating speed of 4500r/min for 10min after cooling to obtain a cassava starch solution; (2) stirring 30.0-50.0g of epidesmine powder and 90-150ml of HCl solution with the mass percent concentration of 15% at the temperature of 70-90 DEG C for 1-3h, filtering, washing until no Cl<-> exists, and drying to form acidized zeolite; (3) mixing 6.0-10.0g of NaOH and 3.0-5.0g of NaAlO2, adding 144-240ml of water, adding 3.0-5.0g of acidized zeolite, stirring, crystallizing, filtering, washing and drying to obtain a zeolite A molecular sieve; (4) keeping 20mL of cassava starch solution and 2.5-3.5g of zeolite A molecular sieve at the temperature of 10-30 DEG C for 1-2h, centrifuging at the rotating speed of 4500r/min for 10min, and settling. The starch zeolite molecular sieve flocculating agent prepared by using the preparation method is favorable in performance, is nontoxic and harmless and has a broad spectrum effect; when the flocculating agent is used for purifying water, the water purification rate is up to 97.41%.
Description
Technical field
The invention belongs to biological environmental production technical field, relate to a kind of preparation method of starch zeolite molecular sieve flocculation agent.
Background technology
Inorganic flocculating agent, Syn-Organic flocculants and natural macromolecule flocculating agent are three large main flow flocculation agents of water treatment field, but the pollution again that the water-soluble rear ion residues of inorganic flocculating agent causes, the expensive and carinogenicity of synthetic polymeric flocculant has limited the application of this two classes flocculation agent.Starch is reproducible natural polymer, and price is low, source is wide, nontoxic.On starch main chain, introducing the side chain with more active group by appropriate means, both brought into play the advantage of itself, make again it meet the requirement of flocculation, is one of important development direction of natural macromolecule flocculating agent.
The kind of the flocculation agent of research is a lot of at present, and starch is organic polymer coargulator material conventional in water treatment, forms multipolymer for wastewater treatment with polyacrylamide.Cao Ping Ming etc. are by tapioca (flour), vinyl monomer, catalyst reaction, add again aldehydes and alcohols reaction, make novel cation CS-1 flocculation agent, redox initiator for fence Song Han etc., synthesize cationic starch flocculant taking tapioca (flour) as raw material, and studied the structure of graft polyacrylamide polymeric flocculant and the relation of performance.Zhao Yansheng etc. have studied employing single stage method and have carried out SGM modification and prepare cationic flocculant CSGM, determine that optimised process is 50 DEG C, 2h.This flocculation agent is better to disposal effect of dyeing wastewater.Starch base phosphoric acid ester is a kind of good anionic starch flocculation agent, and Zhang Shuyuan etc. are by cross-linking starch xanthate for the treatment of the electroplating wastewater containing chromium, and decreasing ratio can reach more than 95%, and chromium residual concentration is less than 0.2mg/L; Experimental result shows, processes the electroplating wastewater containing chromium with cross-linking starch xanthate flocculation agent, the decreasing ratio of chromium ion is greater than to 99%, and residue stability is high, can not cause the secondary pollution of environment.Phase waves etc. are taking W-Gum as raw material, HClO
4make initiator, epoxy chloropropane is made etherifying agent, synthetic mesophase product 3-chlorine-2-hydroxyl propenyl cross-linking starch, then this cross-linking starch is reacted with quadrol under alkaline condition, the amino starch CAS that obtains having chelate structure, this cross-linking starch is strong to the adsorptivity of cupric ion.Quan Yi etc. by after W-Gum and epoxy chloropropane crosslinking reaction again with chloroacetate reaction, obtain carboxymethyl cross-linking starch (CCMS), this flocculation agent is to having good flocculating effect containing heavy metal and containing aniline waste water.Quan Yi etc. are at initiator Ce
4+effect under by acrylonitrile grafting to starch, then change itrile group into carboxyl by alkali saponification and make starch graft copolymer, this multipolymer has better adsorption to the heavy metal ion in waste water.Yang Bo etc. utilize this physical means of 60Co-gamma-rays to cause starch and acrylamide generation graft copolymerization, study the rule of radiation initiation grafting copolymerization, and explore the relation of irradiation time and percentage of grafting, and irradiation dose, irradiation temperature, monomer concentration, the impact of starch concentration on grafting Copolycondensation rate, inquire into the mechanism of graft copolymerization, the production practice of macromolecular grafted reaction have been had to certain realistic meaning.Zhu Ruiyi etc. are taking W-Gum, acrylamide, Acrylic Acid Monomer as raw material, ceric ammonium nitrate is as initiator, prepare W-Gum graft copolymer, studied the impact on grafting efficiency and grafts performance of ceric ammonium nitrate concentration, monomer concentration and concentration of nitric acid, result shows that two kinds of multipolymers of preparation have good flocculating effect to kaolin.Li Xuxiang etc. make initiator with ammonium persulphate, make vinyl cyanide and water caltrop starch graft copolymerization, study the impact of monomer concentration on graft reaction, the initiation effect of more different initiators, it is best that result shows to make initiator effect with ammonium persulphate, and multipolymer treatment of dyeing and printing has obtained good effect.Li Shuhong etc. make initiator with ceric ammonium nitrate, by the modification synthetic polymeric flocculant (FSM) to starch, the oil field waste of high salinity are processed with FSM, and result shows that this flocculation agent has and good go turbid and go COD performance oil field waste.Chang Wenyue etc. cause free radical by potassium permanganate/oxalic acid, by acrylamide graft to starch; Result shows: this flocculation agent has stronger adsorptive power to the multiple sewage such as municipal effluent, trade effluent, is a kind of starch flocculant of cheap, superior performance.Wang Xin etc. adopt the direct graft polymerization reaction of starch and polyacrylamide (PAM), with low cost, technique is simple, and test-results shows that this polymer treatment dyeing waste water has good effect.L. Jarnstrom etc. is taking yam starch as raw material, be oxidized with hypochlorite, after stable, carry out cationization, prepare a kind of quaternary amine starch ethers, and with fibre optics Research on Sensing flocculating effect, find that this cationic starch, within the scope of 23-50 DEG C, has good throwing out to kaolin suspension liquid.Above-mentioned research is chemical reagent and starch-grafted, copolymerization, crosslinked.In preparation and use procedure, human body and environment are had to adverse influence.Stellerite is natural inorganic materials, has no side effect.Utilize at present stellerite molecular sieve and starch adsorption or grafting have not been reported.
Natural zeolite is a kind of moisture basic metal of frame columnar structure or manosil AS mineral of alkaline-earth metal of being.As a kind of nonmetal mineral resource, the reserves of China enrich very much, and total reserves reaches 10,000,000,000 tons.Special pore passage structure and chemical property make zeolite have ion-exchange, select excellent properties and the environment attributes such as absorption, catalysis, are therefore in experimental study or practical application, all to have obtained development rapidly.The treatment technology of nitrogen-containing wastewater mainly contains biosynthesizing nitrofication process, ion exchange method, air vapor vaporizing extract process, chlorination and absorption, chemical precipitation method etc., and zeolite has larger adsorptive capacity to ammonia nitrogen, natural zeolite is a kind of novel cheap ion-exchanger of removing the heavy metal ion such as copper, mercury, lead and zinc.
Starch is organic polymer coargulator conventional in water treatment, it is by many glucose molecules polymeric carbohydrate being polymerized that dewaters, have many side chains, straight chain and hydroxyl, relative molecular weight is about between 50,000 to 150,000, has stronger retrogradation performance.By the modification of the methods such as physics, chemistry, biology, the chemical structure that can change some D-glucopyranose units in starch molecule obtains efficient modified starch flocculant, as water treatment, its selectivity is large, nontoxic, can be biodegradable completely, form good circulation at occurring in nature.External water treatment has many ameliorative starch flocculants on market.
Flocculence is the important method of water technology, and its matter of utmost importance is that processability is good, reasonable price, have the flocculation agent of wide spectrum effect.Cheap practical, the nontoxic or low toxicity efficient flocculant of exploitation is the developing direction of flocculation agent from now on targetedly.Particularly develop nontoxic, efficient, degradable, and not have the natural of secondary pollution or flocculation flocculation agent be the trend of flocculation development.
Summary of the invention
The object of this invention is to provide a kind of excellent property, reasonable price, there is the preparation method of the starch zeolite molecular sieve flocculation agent of wide spectrum effect.
Concrete steps are:
(1) take 2.0-10.0 gram of tapioca (flour), add distilled water to stir into pasty state, then limit adds the stirring of boiling water limit, finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0-50.0 gram of stellerite powder and 90-150 milliliter mass percent concentration mixes, and in 70-90 DEG C, electric stirring 1-3 hour, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 6.0-10.0 gram of NaOH and 3.0-5.0 gram of NaAlO
2mix and add 144-240 ml water, be mixed with solution, then add the acidifying zeolite of 3.0-5.0 gram of step (2) gained, magnetic agitation, crystallization temperature 80-100 DEG C, crystallization time 5-7 hour, product after filtration, washing, dry after obtain A type zeolite molecular sieve (Na
2oAl
2o
32SiO
24.5H
2o).
(4) 20mL step (1) gained tapioca (flour) solution and 2.5-3.5 gram of step (3) gained A type zeolite molecular sieve are mixed, be placed in 10-30 DEG C of insulation 1-2 hour in constant temperature blender with magnetic force, 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculate the absorption of A type zeolite molecular sieve or graft starch amount.
A type zeolite molecular sieve and tapioca (flour) formation multipolymer are prepared flocculation agent by the present invention, and its structure is characterized, and processing condition are optimized; The starch zeolite molecular sieve flocculation agent of preparation, can be applicable to the processing of industry or sanitary wastewater, also can be applicable to, in microbial fermentation solution or effective ingredients in plant leaching process, can realize class settling according to the density of this flocculation agent, reaches the object of separation and purification.This flocculation agent excellent property, nontoxic, has wide spectrum effect, has good application prospect.Purify waste water with this flocculation agent, water purification rate reaches 97.41%.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the infrared spectrogram of the A type zeolite molecular sieve prepared of the embodiment of the present invention 1, and the characteristic peak of Fig. 2 description architecture hydroxyl and physical absorption water is positioned at 3 435 cm
– 1with 1 644cm
– 1; [SiO
4] [AlO
4] tetrahedral symmetrical stretching vibration and antisymmetric stretching vibration peak position be in 1 015 cm
– 1with 694 cm
– 1; [SiO
4] [AlO
4] flexural vibration peak position between tetrahedron is in 448 cm
– 1.
Fig. 3 is the infrared spectrogram of the tapioca (flour) of use in the embodiment of the present invention 1, can find out 3412 cm
– 1there is strong and wide tapioca (flour) glucose unit-OH stretching vibration Absorption Characteristics peak, 2931 cm
– 1the C-CH of place
2the asymmetrical stretching vibration of-C; 1159 cm
– 1the C-O-C of place asymmetrical stretching vibration; 1647 cm
– 1, 1401 cm
– 1, 1159 cm
– 1, 1081 cm
– 1, 993 cm
– 1place is for C-O key is symmetrical and asymmetrical stretching vibration absorption peak; At 929cm
-1, 861 cm
-1, 765 cm
-1, 710 cm
-1, 574 cm
-1, 529 cm
-1be its charateristic avsorption band at place.
Fig. 4 is the infrared spectrogram of the starch zeolite molecular sieve flocculation agent prepared of the embodiment of the present invention 1, in figure in the absorption peak that contains A type zeolite molecular sieve, 2936 cm
– 1there is tapioca (flour) C-CH in place
2the asymmetrical stretching vibration of-C; 1648 cm
– 1, 1401 cm
-1there is the C-O key symmetry and asymmetrical stretching vibration absorption peak of tapioca (flour) in place; At fingerprint region 695 cm
-1, 660 cm
-1, 556 cm
-1, 460 cm
-1there is the charateristic avsorption band of tapioca (flour) and A type zeolite molecular sieve at place.From its constitutional features, prove the generation of flocculation agent.
Embodiment
Utilize orthogonal design table, determine optimised process.Each level of factor is in table 1, and orthogonal experiment is in table 2.
Table 1 factor and level design:
Table 2 orthogonal experiment L
9(3
3) table:
Embodiment 1:
(1) take 2.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0 grams of stellerite powder and 90 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 90 DEG C, electric stirring 2 hours, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 8.0 grams of NaOH and 4.0 grams of NaAlO
2mix and add 192 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 4.0 grams of steps (2) gained, magnetic agitation, 90 DEG C of crystallization temperatures and crystallization time 6 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 3.5 grams of steps (3) gained, be placed on shaking table 30 DEG C of insulations of constant temperature 1 hour, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 32.165mg.
The mensuration of starch zeolite molecular sieve flocculation agent purifying water effect:
(1) utilize GB potassium dichromate process to measure the chemical oxygen demand (COD) of waste water: the backflow Erlenmeyer flask of getting trade effluent water sample that 20.00mL mixes and be placed in 250mL ground, accurately add 10.00mL potassium bichromate standardized solution and several little granulated glass spherees, connect ground reflux condensing tube, from the prolong 30 mL sulfuric acid-silver sulfate solutions that add at leisure suitable for reading, shake gently Erlenmeyer flask solution is mixed, reflux 2 hours (timing while certainly coming to life).After cooling, with 90mL water flushing condensation tube wall, take off Erlenmeyer flask.Overall solution volume must not be less than 140mL, otherwise because acidity is too large, titration end point is not obvious.After solution is cooling once again, add 3 phenanthroline ion indicating liquids, with the titration of ferrous ammonium sulphate standardized solution, the color of solution is terminal by yellow through blue-greenish colour to sorrel, records the consumption of ferrous ammonium sulphate standardized solution.When measuring water sample, get 20.00mL double distilled water, do blank test by same operation steps.The consumption of ferrous ammonium sulphate standardized solution while recording titration blank, according to the chemical oxygen demand (COD) of formula calculating raw wastewater.
(2) separately get trade effluent 20mL, add starch zeolite flocculation agent 2.0mg, adjusting pH is 4, and water temperature is 25 DEG C, places 1 hour.Filter, get supernatant liquor and be purified water, measure with (1) described method the chemical oxygen demand (COD) of purifying waste water, calculate the chemical oxygen demand value of purifying waste water according to formula, determine the performance of purifying waste water of flocculation agent.
(3) flocculation agent adsorption effect: chemical oxygen demand (COD) 528 mg/mL of raw wastewater, chemical oxygen demand (COD) 13.67 mg/mL of water after flocculation agent purifies, water purification rate 97.41%.
Embodiment 2:
(1) take 5.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 40.0 grams of stellerite powder and 120 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 80 DEG C, electric stirring 1 hour, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 10.0 grams of NaOH and 5.0 grams of NaAlO
2mix and add 240 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 5.0 grams of steps (2) gained, magnetic agitation, 100 DEG C of crystallization temperatures and crystallization time 7 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 3.0 grams of steps (3) gained, be placed on shaking table 20 DEG C of insulations of constant temperature 1 hour, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 24.070mg.
Embodiment 3:
(1) take 2.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0 grams of stellerite powder and 90 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 90 DEG C, electric stirring 2 hours, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 8.0 grams of NaOH and 4.0 grams of NaAlO
2mix and add 192 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 4.0 grams of steps (2) gained, magnetic agitation, 90 DEG C of crystallization temperatures and crystallization time 6 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 2.5 grams of steps (3) gained, be placed on shaking table 10 DEG C of insulations of constant temperature 1 hour, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 30.658mg.
Embodiment 4:
(1) take 2.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0 grams of stellerite powder and 90 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 90 DEG C, electric stirring 2 hours, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 8.0 grams of NaOH and 4.0 grams of NaAlO
2mix and add 192 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 4.0 grams of steps (2) gained, magnetic agitation, 90 DEG C of crystallization temperatures and crystallization time 6 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 3.5 grams of steps (3) gained, be placed on shaking table 10 DEG C of insulations of constant temperature 1.5 hours, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 31.672mg.
Embodiment 5:
(1) take 2.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0 grams of stellerite powder and 90 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 90 DEG C, electric stirring 2 hours, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 8.0 grams of NaOH and 4.0 grams of NaAlO
2mix and add 192 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 4.0 grams of steps (2) gained, magnetic agitation, 90 DEG C of crystallization temperatures and crystallization time 6 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 2.5 grams of steps (3) gained, be placed on shaking table 20 DEG C of insulations of constant temperature 1.5 hours, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 28.631mg.
Embodiment 6:
(1) take 2.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0 grams of stellerite powder and 90 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 90 DEG C, electric stirring 2 hours, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 8.0 grams of NaOH and 4.0 grams of NaAlO
2mix and add 192 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 4.0 grams of steps (2) gained, magnetic agitation, 90 DEG C of crystallization temperatures and crystallization time 6 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 3.0 grams of steps (3) gained, be placed on shaking table 30 DEG C of insulations of constant temperature 1.5 hours, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 23.437mg.
Embodiment 7:
(1) take 2.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0 grams of stellerite powder and 90 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 90 DEG C, electric stirring 2 hours, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 8.0 grams of NaOH and 4.0 grams of NaAlO
2mix and add 192 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 4.0 grams of steps (2) gained, magnetic agitation, 90 DEG C of crystallization temperatures and crystallization time 6 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 3.0 grams of steps (3) gained, be placed on shaking table 10 DEG C of insulations of constant temperature 2 hours, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 22.930mg.
Embodiment 8:
(1) take 2.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0 grams of stellerite powder and 90 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 90 DEG C, electric stirring 2 hours, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 8.0 grams of NaOH and 4.0 grams of NaAlO
2mix and add 192 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 4.0 grams of steps (2) gained, magnetic agitation, 90 DEG C of crystallization temperatures and crystallization time 6 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 2.5 grams of steps (3) gained, be placed on shaking table 20 DEG C of insulations of constant temperature 2 hours, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 24.450mg.
Embodiment 9:
(1) take 2.0 grams of tapioca (flour)s and put into the beaker of 500mL, add distilled water to stir into pasty state, then limit adds boiling water limit and stirs, and finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution.
(2) the HCl solution that is 15% by 30.0 grams of stellerite powder and 90 milliliters of mass percent concentrations is placed in 250mL three-necked bottle, and in 90 DEG C, electric stirring 2 hours, filters, and washing is to without Cl
-, be dried into acidifying zeolite.
(3) by 8.0 grams of NaOH and 4.0 grams of NaAlO
2mix and add 192 ml waters, be mixed with solution, add in three-necked bottle, then add the acidifying zeolite of 4.0 grams of steps (2) gained, magnetic agitation, 90 DEG C of crystallization temperatures and crystallization time 6 hours, product after filtration, washing, obtain A type zeolite molecular sieve (Na after drying
2oAl
2o
32SiO
24.5H
2o).
(4) get 100mL Erlenmeyer flask, add the tapioca (flour) solution of 20mL step (1) gained and the A type zeolite molecular sieve of 3.5 grams of steps (3) gained, be placed on shaking table 30 DEG C of insulations of constant temperature 2 hours, then 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.Utilize anthrone colorimetry to survey starch solution absorbancy, calculating the absorption of A type zeolite molecular sieve or graft starch amount is 22.677mg.
Claims (1)
1. a preparation method for starch zeolite molecular sieve flocculation agent, is characterized in that concrete steps are:
(1) take 2.0-10.0 gram of tapioca (flour), add distilled water to stir into pasty state, then limit adds the stirring of boiling water limit, finally reheats boiling, and cooling latter 4500 revs/min, centrifugal 10 minutes, get supernatant liquor, obtain tapioca (flour) solution;
(2) the HCl solution that is 15% by 30.0-50.0 gram of stellerite powder and 90-150 milliliter mass percent concentration mixes, and in 70-90 DEG C, electric stirring 1-3 hour, filters, and washing is to without Cl
-, be dried into acidifying zeolite;
(3) by 6.0-10.0 gram of NaOH and 3-5 gram of NaAlO
2mix and add 144-240 ml water, be mixed with solution, then add the acidifying zeolite of 3.0-5.0 gram of step (2) gained, magnetic agitation, crystallization temperature 80-100 DEG C, crystallization time 5-7 hour, product is after filtration, washing, to obtain A type zeolite molecular sieve be Na after drying
2oAl
2o
32SiO
24.5H
2o;
(4) 20mL step (1) gained tapioca (flour) solution and 2.5-3.5 gram of step (3) gained A type zeolite molecular sieve are mixed, be placed in 10 DEG C-30 DEG C insulation 1-2 hour in constant temperature blender with magnetic force, 4500 revs/min, centrifugal 10 minutes, precipitation was starch zeolite molecular sieve flocculation agent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106219696A (en) * | 2016-08-12 | 2016-12-14 | 伍德广聚（北京）环境科技有限公司 | A kind of composite flocculation agent |
| CN107986417A (en) * | 2017-12-28 | 2018-05-04 | 安徽宏实光机电高科有限公司 | A kind of preparation method of Sewage sepiolite/starch grafted polyacrylamide composite flocculation agent |
| CN109731103A (en) * | 2019-01-20 | 2019-05-10 | 桂林理工大学 | P-zeolite-chitin-sodium alginate-potassium diformate sustained-release antibacterial agent preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002273103A (en) * | 2001-03-19 | 2002-09-24 | Etsuro Sakagami | Artificial zeolite compounded flocculant and sewage treatment method using the same |
| CN101628748A (en) * | 2009-07-16 | 2010-01-20 | 淮南市蔚蓝水处理技术有限公司 | Composite macromolecule coagulant for water purification |
| CN102092826A (en) * | 2010-11-26 | 2011-06-15 | 淮南市蔚蓝水处理技术有限公司 | Environmental-friendly type coagulant for purifying water |
| CN103508536A (en) * | 2013-10-15 | 2014-01-15 | 江苏商达水务有限公司 | Sewage treatment flocculating agent in livestock farm |
-
2014
- 2014-03-28 CN CN201410121902.0A patent/CN103864193B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002273103A (en) * | 2001-03-19 | 2002-09-24 | Etsuro Sakagami | Artificial zeolite compounded flocculant and sewage treatment method using the same |
| CN101628748A (en) * | 2009-07-16 | 2010-01-20 | 淮南市蔚蓝水处理技术有限公司 | Composite macromolecule coagulant for water purification |
| CN102092826A (en) * | 2010-11-26 | 2011-06-15 | 淮南市蔚蓝水处理技术有限公司 | Environmental-friendly type coagulant for purifying water |
| CN103508536A (en) * | 2013-10-15 | 2014-01-15 | 江苏商达水务有限公司 | Sewage treatment flocculating agent in livestock farm |
Non-Patent Citations (2)
| Title |
|---|
| L. JARNSTROM ET AL.: "Flocculation in kaolin suspensions induced by modified starches 1. Cationically modified starch effects of temperature and ionic strength", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS 》 * |
| 杨波等: "淀粉和丙烯酰胺的辐照接枝共聚反应研究", 《高分子材料科学与工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106219696A (en) * | 2016-08-12 | 2016-12-14 | 伍德广聚（北京）环境科技有限公司 | A kind of composite flocculation agent |
| CN107986417A (en) * | 2017-12-28 | 2018-05-04 | 安徽宏实光机电高科有限公司 | A kind of preparation method of Sewage sepiolite/starch grafted polyacrylamide composite flocculation agent |
| CN109731103A (en) * | 2019-01-20 | 2019-05-10 | 桂林理工大学 | P-zeolite-chitin-sodium alginate-potassium diformate sustained-release antibacterial agent preparation method |
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