CN103861566A - Preparation method of efficiently-adsorptive modified starch microspheres and application of modified starch microspheres - Google Patents
Preparation method of efficiently-adsorptive modified starch microspheres and application of modified starch microspheres Download PDFInfo
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Abstract
The invention discloses a preparation method of efficient-adsorption modified starch microspheres, adsorptive modified starch microspheres prepared by the method and an application method of the modified starch microspheres. According to the preparation method, starch, carbamide and phosphoric acid are synthesized at a certain reaction condition to obtain phosphoric acid-starch carbamate, thus greatly improving the adsorbing capacity; meanwhile, a urethane group is introduced, so that the water solubility of the phosphoric acid-starch carbamate is improved, thereby influencing the separation between the phosphoric acid-starch carbamate and a water solution. According to the preparation method, starch microspheres are prepared firstly, and then phosphoric acid-starch carbamate starch microspheres are prepared through a one-step method by taking the starch microspheres, carbamide, phosphoric acid and sodium citrate as raw materials. Due to the adoption of microsphere molecules, the adsorbing capacity is greatly improved. The modified starch microspheres prepared by the method is especially applicable to adsorption treatment of printing and dyeing wastewater.
Description
Technical field
The present invention relates to a kind of preparation method and application of efficient adsorption modified starch microspheres, belong to water treatment agent preparing technical field.Modified starch microspheres prepared by the present invention is specially adapted to the adsorption treatment of dyeing waste water.
Background technology
Printing and dyeing are earned foreign exchange in important industry becoming China's export, also become one of industry of high energy consumption, high pollution, and average every production 1 kg product needed consumes 0.2～0.5 m
3water, and in dyeing waste water, contain dyestuff, slurry, auxiliary agent, acid, alkali, fiber impurity and inorganic salts etc., colourity is very big, is difficult to process.Particularly in recent years, the stability of dye structure greatly improved, and had further increased decolouring difficulty.The method of dye wastewater treatment using mainly contains chemical oxidization method, flocculent precipitation, bioanalysis and physisorphtion etc., wherein chemical oxidization method can destroy the aromatic ring structure of dyestuff, but it can produce more chemical sludge and may generate the intermediate product that toxicity is larger in processing procedure; Flocculent precipitation dosing is large, complicated operation, sludge quantity is large and can only remove the COD of 60% left and right; It is large to improve its biodegradability and floor space that bioanalysis need to carry out pretreatment; Physisorphtion is due to its concern that is subject to vast researcher compared with high treatment effeciency, seeks that adsorbance is large, low toxicity noresidue, adsorbent that power of regeneration is strong become current study hotspot.
Natural modified adsorbent because its raw material sources are abundant, cheap, the selective feature such as good, safety non-toxic, fully biodegradable, and receive much concern.Starch is the macromolecule natural products being formed by connecting through glycosidic bond by many dehydrated glucose units, on 2,3,6 three positions of each dehydrated glucose unit, respectively there is an alcoholic extract hydroxyl group, under initator effect, on starch, hydroxyl and crosslinking agent carry out the appropriately crosslinked spherex that makes.Research shows, spherex has dilation, sizable pore volume and the specific area of good biocompatibility, biodegradable, appropriateness, is a kind ofly to have compared with the adsorbent of great development potentiality.But in waste water treatment applications, find that spherex exists two technical barriers: (1) spherex mainly relies on pore volume and specific area performance physisorption, and adsorption reaction active site is single, limited to the adsorbance of pollutant.(2) degree of cross linking deficiency of microsphere particles stratum nucleare and shell, in the time that the environmental condition such as temperature, pH changes, that spherex easily occurs is swelling, shrink or dissolve and make reactivity point by embedding or lose, and the pollutant of original absorption is discharged again.
Summary of the invention
The present invention seeks to the absorption property in order to improve spherex, a kind of preparation method of efficient adsorption modified starch microspheres is provided, the technical problem that the present invention solves comprises:
(1) in the building-up process of spherex, improve the degree of cross linking of microsphere particles stratum nucleare and shell, construct network-like molecular structure, strengthen nucleocapsid intermolecular force large, improve the chemical stability of microballoon, strengthen the adaptability of microballoon to the environmental condition such as temperature, pH, the desorb of pollutant occurs while avoiding changes in environmental conditions.
(2) spherex active group is carried out to modification, introduce ionic group, the suction-operated such as ion-exchange, chelating mode is occurred simultaneously, improve coordination and Electrostatic Absorption ability, increase adsorption activity site, improve the adsorbance to pollutant.
The preparation method who the invention provides a kind of efficient adsorption modified starch microspheres, comprises the steps:
(1) preparation of spherex
Be 1:1.4-1.6(weight ratio by starch and water) be fully mixed to get compound, add again described compound 0.5-0.8%(weight ratio) NaCl and 4-5%(volume ratio) epoxychloropropane, regulate pH value to 11.0-12.0, stirring reaction 15-20 hour, then regulate pH value to 6.0, staticly settle, sediment first washes with water 2-4 time, wash 2-4 time with 70% alcohol again, last suction filtration, solids obtains spherex after 60-70 DEG C of oven for drying.
(2) sex change of spherex
By urea: 85% phosphoric acid: natrium citricum=5-25:0.75-3:1 (weight ratio) mixes, add the ethanol of described compound 30-40%, fully stir, the spherex that adds again described compound 110-170%, stirs, and is placed in the microwave-oven-heating 2-5 minute of 650-750w, product washes with water 2-4 time, wash 2-4 time with 70% alcohol again, last suction filtration, solids obtains modified starch microspheres after 60-70 DEG C of oven for drying.
In above-mentioned steps (1), starch is one or more mixture of cornstarch, farina, wheaten starch.
In above-mentioned steps (1), adopt NaOH, vinegar acid for adjusting pH value.
In above-mentioned steps (2), microwave adopts the intermittent heating, i.e. every heating intermittently 5 seconds in 10 seconds.
The using method of modified starch microspheres of the present invention is as follows:
Regulate dyeing waste water pH to 5.0-10.0(alkali to select calcium hydroxide with alkali or acid, sulfuric acid or hydrochloric acid are selected in acid), every 1000mL waste water adds 0.4-0.6g modified starch microspheres, vibrate 1 hour, then within static 30 minutes, gets supernatant mensuration CODCr and colourity.CODCr clearance reaches more than 55%, and percent of decolourization reaches more than 92%.
The present invention has following beneficial effect:
The present invention first prepares spherex, then taking spherex, urea, phosphoric acid, natrium citricum as raw material, adopts one-step method to prepare phosphoric acid-starch carbamates microballoon.The present invention compared with prior art tool has the following advantages and effect:
(1) first synthetic starch microballoon, recycling spherex and urea effect generate starch carbamate, produce crosslinked action, construct network-like molecular structure, strengthen intermolecular force large, improved chemical stability, strengthened mechanical strength, anti-shearing force and the stability to soda acid increase substantially; Meanwhile, it is phosphate-based that microballoon intramolecule is introduced anionic group, increased adsorption activity site, greatly improved adsorbance.
(2) in spherex, urea and phosphatase reaction process, urea starts to decompose release ammonia near being heated to its fusing point, catabolite isocyanic acid and starch reaction generate starch carbamates ester, and numerous side reactions has affected the character of reaction efficiency and the product of urea.By adding the amino on natrium citricum and urea to produce bonding action, control urea and slowly decompose, the generation of restriction side reaction, thus improve reaction efficiency.
Detailed description of the invention
Detailed description below by detailed description of the invention is further illustrated the present invention, but is not limitation of the present invention, only does example explanation.
embodiment 1
(1) 100 g starch are joined in 140ml water, after stirring, add the epoxychloropropane of 1.2 g sodium chloride and 9.6mL, utilize NaOH solution to regulate pH value to 11.0, stirring reaction 16 hours, then use second acid for adjusting pH value to 6.0, staticly settle, sediment first washes with water 2 times, wash 4 times with 70% alcohol again, last suction filtration, solids obtains spherex after 60 DEG C of oven for drying.
(2) 20 grams of urea, 2mL 85% phosphoric acid, 2 grams of natrium citricums are fully mixed, add 7mL ethanol, be stirred to urea and natrium citricum dissolves completely, add again 26 grams of spherexs, stir, be placed in 5 minutes (every heating intermittently 5 seconds in 10 seconds) of microwave-oven-heating of 650w, product washes with water 3 times, wash 4 times with 70% alcohol again, last suction filtration, solids obtains modified starch microspheres after 70 DEG C of oven for drying.
(3) in 500mL crystal violet dyeing waste water, drip dilute sulfuric acid pH value is adjusted to 5.0, add 0.2g modified starch microspheres, vibrate 1 hour, then within static 30 minutes, get supernatant and measure COD
crand colourity.COD
crclearance reaches 52.9%, and percent of decolourization reaches 92.5%.
embodiment 2
(1) 100 g starch are joined in 150ml water, after stirring, add the epoxychloropropane of 1.5 g sodium chloride and 10mL, utilize NaOH solution to regulate pH value to 12.0, stirring reaction 15 hours, then use second acid for adjusting pH value to 6.0, staticly settle, sediment first washes with water 4 times, wash 2 times with 70% alcohol again, last suction filtration, solids obtains spherex after 70 DEG C of oven for drying.
(2) 20 grams of urea, 3mL85% phosphoric acid, 4 grams of natrium citricums are fully mixed, add 8mL ethanol, be stirred to urea and natrium citricum dissolves completely, add again 35 grams of spherexs, stir, be placed in 2 minutes (every heating intermittently 5 seconds in 10 seconds) of microwave-oven-heating of 650w, product washes with water 2 times, wash 4 times with 70% alcohol again, last suction filtration, solids obtains modified starch microspheres after 60 DEG C of oven for drying.
(3) in 500mL crystal violet dyeing waste water, drip dilute sulfuric acid pH value is adjusted to 7.0, add 0.25g modified starch microspheres, vibrate 1 hour, then within static 30 minutes, get supernatant and measure COD
crand colourity.COD
crclearance reaches 54.8%, and percent of decolourization reaches 95.8%.
embodiment 3
(1) 100 g starch are joined in 160ml water, after stirring, add the epoxychloropropane of 1.8 g sodium chloride and 13mL, utilize NaOH solution to regulate pH value to 11.0, stirring reaction 20 hours, then use second acid for adjusting pH value to 6.0, staticly settle, sediment first washes with water 3 times, wash 3 times with 70% alcohol again, last suction filtration, solids obtains spherex after 60 DEG C of oven for drying.
(2) 25 grams of urea, 3mL85% phosphoric acid, 1 gram of natrium citricum are fully mixed, add 12mL ethanol, be stirred to urea and natrium citricum dissolves completely, add again 44 grams of spherexs, stir, be placed in 4 minutes (every heating intermittently 5 seconds in 10 seconds) of microwave-oven-heating of 750w, product washes with water 3 times, wash 4 times with 70% alcohol again, last suction filtration, solids obtains modified starch microspheres after 65 DEG C of oven for drying.
(3) in 500mL crystal violet dyeing waste water, drip dilute sulfuric acid pH value is adjusted to 8.0, add 0.3g modified starch microspheres, vibrate 1 hour, then within static 30 minutes, get supernatant and measure COD
crand colourity.COD
crclearance reaches 56.5%, and percent of decolourization reaches 98.8%.
embodiment 4
(1) 100 g starch are joined in 140ml water, after stirring, add the epoxychloropropane of 1.9 g sodium chloride and 12mL, utilize NaOH solution to regulate pH value to 12.0, stirring reaction 18 hours, then use second acid for adjusting pH value to 6.0, staticly settle, sediment first washes with water 2 times, wash 4 times with 70% alcohol again, last suction filtration, solids obtains spherex after 65 DEG C of oven for drying.
(2) 30 grams of urea, 3mL85% phosphoric acid, 2 grams of natrium citricums are fully mixed, add 14mL ethanol, be stirred to urea and natrium citricum dissolves completely, add again 60 grams of spherexs, stir, be placed in 5 minutes (every heating intermittently 5 seconds in 10 seconds) of microwave-oven-heating of 700w, product washes with water 3 times, wash 3 times with 70% alcohol again, last suction filtration, solids obtains modified starch microspheres after 65 DEG C of oven for drying.
(3) in 500mL crystal violet dyeing waste water, drip dilute sulfuric acid pH value is adjusted to 10.0, add 0.3g modified starch microspheres, vibrate 1 hour, then within static 30 minutes, get supernatant and measure COD
crand colourity.COD
crclearance reaches 55.3%, and percent of decolourization reaches 96.6%.
Claims (8)
1. a preparation method for efficient adsorption modified starch microspheres, comprises the steps:
The preparation of spherex
Be 1:1-1:2(weight ratio by starch and water) be fully mixed to get compound, add again described compound 0.5-0.8%(weight ratio) NaCl and 4-5%(volume ratio) epoxychloropropane, regulate pH value to 11.0-12.0, stirring reaction 15-20 hour, then regulate pH value to 6.0, staticly settle, sediment first washes with water 2-4 time, wash 2-4 time with 70% alcohol again, last suction filtration, solids obtains spherex after 60-70 DEG C of oven for drying;
(2) sex change of spherex
By urea: 85% phosphoric acid: natrium citricum=5-25:0.75-3:1 (weight ratio) mixes, add the ethanol of described compound 30-40%, fully stir, the spherex that adds again described compound 110-170%, stirs, and is placed in the microwave-oven-heating 2-5 minute of 650-750w, product washes with water 2-4 time, wash 2-4 time with 70% alcohol again, last suction filtration, solids obtains modified starch microspheres after 60-70 DEG C of oven for drying.
2. preparation method according to claim 1, is characterized in that, the described starch in step (1) is one or more mixture of cornstarch, farina, wheaten starch.
3. preparation method according to claim 1 and 2, is characterized in that, the described starch in step (1) and the ratio of water are 1:1.2-1:1.6.
4. preparation method according to claim 1 and 2, is characterized in that, adopts NaOH, vinegar acid for adjusting pH value in step (1).
5. preparation method according to claim 1 and 2, is characterized in that, in step (2), microwave-oven-heating adopts the intermittent heating.
6. according to the efficient adsorption modified starch microspheres making of preparation method described in any one in claim 1 to 5.
7. the using method of efficient adsorption modified starch microspheres according to claim 6, it is characterized in that: with alkali or acid adjusting dyeing waste water pH to 5.0-10.0, every 1000mL waste water adds 0.4-0.6g modified starch microspheres, vibrate 1 hour, then within static 30 minutes, get supernatant and measure CODCr and colourity.
8. the using method of efficient adsorption modified starch microspheres according to claim 7, is characterized in that: described alkali is calcium hydroxide, and described acid is sulfuric acid or hydrochloric acid.
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Cited By (5)
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| CN105567626A (en) * | 2016-02-24 | 2016-05-11 | 冯玉萍 | Micro-carrier for cell culture and preparation method and application thereof |
| CN105944690A (en) * | 2016-07-14 | 2016-09-21 | 四川大学 | Biomass adsorbent and preparing method and application thereof |
| CN109422817A (en) * | 2017-08-22 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of micron-level crosslinked spherex and its preparation method and application |
| CN110066347A (en) * | 2019-05-23 | 2019-07-30 | 齐齐哈尔大学 | A kind of oxalic acid/phosphoric acid/Jet reactor preparation method |
| CN117401787A (en) * | 2023-11-13 | 2024-01-16 | 山东赛维环保工程有限公司 | Industrial wastewater quality treating agent and application thereof in industrial wastewater treatment |
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| CN101759808A (en) * | 2010-01-14 | 2010-06-30 | 同济大学 | Method for preparing modified polyamine porous starch |
| CN102372785A (en) * | 2010-08-07 | 2012-03-14 | 江苏天麟生物医药科技有限公司 | Simple and feasible method for synthesis of modified starch microspheres in microemulsion system |
| CN102426202A (en) * | 2011-09-15 | 2012-04-25 | 四川大学 | Method for detecting and analyzing trivalent chromium and hexavalent chromium in water sample simultaneously on line |
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Patent Citations (5)
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| US4039444A (en) * | 1976-09-30 | 1977-08-02 | Lever Brothers Company | Water purification device |
| WO2003035561A2 (en) * | 2001-09-10 | 2003-05-01 | Universite Catholique De Louvain | Sustainable process for the treatment and detoxification of liquid waste |
| CN101759808A (en) * | 2010-01-14 | 2010-06-30 | 同济大学 | Method for preparing modified polyamine porous starch |
| CN102372785A (en) * | 2010-08-07 | 2012-03-14 | 江苏天麟生物医药科技有限公司 | Simple and feasible method for synthesis of modified starch microspheres in microemulsion system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105567626A (en) * | 2016-02-24 | 2016-05-11 | 冯玉萍 | Micro-carrier for cell culture and preparation method and application thereof |
| CN105944690A (en) * | 2016-07-14 | 2016-09-21 | 四川大学 | Biomass adsorbent and preparing method and application thereof |
| CN109422817A (en) * | 2017-08-22 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of micron-level crosslinked spherex and its preparation method and application |
| CN109422817B (en) * | 2017-08-22 | 2020-11-06 | 中国石油化工股份有限公司 | Micron-sized crosslinked starch microspheres and preparation method and application thereof |
| CN110066347A (en) * | 2019-05-23 | 2019-07-30 | 齐齐哈尔大学 | A kind of oxalic acid/phosphoric acid/Jet reactor preparation method |
| CN117401787A (en) * | 2023-11-13 | 2024-01-16 | 山东赛维环保工程有限公司 | Industrial wastewater quality treating agent and application thereof in industrial wastewater treatment |
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