CN102225801A - Preparation method of cationized carbamate starch water treatment agent - Google Patents
Preparation method of cationized carbamate starch water treatment agent Download PDFInfo
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- CN102225801A CN102225801A CN2011100978345A CN201110097834A CN102225801A CN 102225801 A CN102225801 A CN 102225801A CN 2011100978345 A CN2011100978345 A CN 2011100978345A CN 201110097834 A CN201110097834 A CN 201110097834A CN 102225801 A CN102225801 A CN 102225801A
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Abstract
The invention relates to a preparation method of a cationized carbamate starch water treatment agent. The method is characterized by comprising the following steps of: 1) raw material selection: selecting raw materials according to the molar ratio of starch to urea to formaldehyde to dimethylamine being 1:1:1:1 and the weight ratio of water to starch being 9:1; 2) preparing starch and water and uniformly mixing to obtain a starch paste; 3) adjusting the pH value to obtain the starch paste with an adjusted pH value; 4) adding urea to obtain a mixture A; 5) raising the temperature of the mixture A to 95-97 DEG C, insulating heat for 1-2 hours and adjusting the pH value to finally obtain a mixture B; 6) adding formaldehyde to obtain a mixture C; 7) cooling the mixture C to 50-55 DEG C, adding dimethylamine and carrying out reaction for 3-5 hours to obtain a mixture D; 8) neutralizing the mixture D with hydrochloric acid till pH reaches 6.5-7.0 to obtain a mixture E; and 9) drying the mixture E obtained in step 8) to obtain the cationized carbamate starch water treatment agent. The water treatment agent prepared by the preparation method has good flocculation effect.
Description
Technical field
The invention belongs to the water conditioner technical field, be specifically related to a kind of preparation method of cationization carbamate starch water conditioner.
Background technology
The amyloid natural carbohydrate output of occurring in nature reaches 5,000 hundreds of millions tons, is the abundantest organic resource that the mankind can take.Starch molecule has a plurality of hydroxyls, crosslinked, graft copolymerization and etherification reaction by these hydroxyls, preparation treated starch water conditioner [Zhan Yali Guo Shao brightness Lv Rong lake. the research and the application of green reagent starch conversion water conditioner. polymer material science and engineering .2003,19 (5): 14-18].At present both at home and abroad the cationic modified starch water conditioner mainly contain acrylamide be principal monomer with ammonium cationoid starch.This type of water conditioner many problems also occurred in the secular application stage, as using various heavy in the flocculation agent preparation process as initiator, especially acrylamide flocculating agent, there is the secondary pollution problem in preparation and the flocculation process, therefore, green, the efficient water conditioner of exploitation is significant.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing cationization carbamate starch water conditioner, the water conditioner of this method preparation has flocculating effect preferably.
For achieving the above object, the technical solution used in the present invention is: prepare the method for cationization carbamate starch water conditioner, it is characterized in that it comprises the steps:
1) choosing of raw material: press starch: urea: formaldehyde: the mol ratio of dimethylamine=1: 1: 1: 1, choose starch, urea, formaldehyde and dimethylamine, press water: the mass ratio of starch=9: 1, choose water, standby;
2) get starch and water stirs evenly, be warming up to 90 ℃, be incubated 5-20 minute,, obtain starch paste starch pasting;
3) with NaOH aqueous solution regulating step 2) pH of the starch paste that obtains is 9.0-11, the starch paste after the adjusted pH value;
4) add urea in the starch paste after regulating the pH value, mixing obtains mixture A;
5) the mixture A that step 4) is obtained is warming up to 95-97 ℃, insulation 1-2h, and regulating pH with formic acid or hydrochloric acid then is 8-9, obtains mixture B;
6) add formaldehyde in the mixture B that step 5) obtains, temperature is reduced to 90-95 ℃, and insulation 30-60min obtains mixture C;
7) mixture C that step 6) is obtained is cooled to 50-55 ℃, adds dimethylamine, and reaction 3-5h obtains mixture D;
8) mixture D being neutralized to pH with hydrochloric acid is 6.5-7.0, obtains mixture E;
9) the mixture E drying that step 8) is obtained obtains cationization carbamate starch water conditioner.
Described starch: urea: formaldehyde: the mol ratio of dimethylamine=1: 1: 1: 1, this proportioning can improve monomeric percentage of grafting on the starch molecule.
The concentration of the described NaOH aqueous solution is 10-30wt%.The concentration of described formic acid is 10-30wt%.The concentration of described hydrochloric acid is 10-30wt%.
The invention has the beneficial effects as follows: the water conditioner of this method preparation has flocculating effect preferably, dispensing dosage is under 10mg/L concentration, the 0.5wt% bentonite suspension of pH about 7 there is good flocculating effect, can clarifies the suspension of 80% volume during flocculation 2min.
The present invention can be used for conglomerate sewage purification such as tap water processing and sanitary sewage, textile sewage, industrial sewage and recycles, and substitutes existing acrylic amide water conditioner, for China's water surrounding purification industry provides product innovation.
Description of drawings
Fig. 1 is the infrared spectrogram of cationization carbamate starch water conditioner.
Fig. 2 is the flocculating effect figure of cationization carbamate starch water conditioner to bentonite suspension.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
Prepare the method for cationization carbamate starch water conditioner, it comprises the steps:
1) choosing of raw material: press starch: urea: formaldehyde: the mol ratio of dimethylamine=1: 1: 1: 1, press water: the mass ratio of starch=9: 1, choose 10g starch, 4.07g urea, 6.8ml formaldehyde, 11.0ml dimethylamine and 90ml water (distilled water), standby;
2) in a four-hole round-bottomed flask that electronic stirring, water condensation and water bath with thermostatic control be housed, get starch and water (distilled water) and stir evenly, be warming up to 90 ℃, be incubated 10 minutes,, obtain starch paste starch pasting;
3) with concentration being the NaOH aqueous solution regulating step 2 of 10wt%, 0.1ml) pH of the starch paste that obtains is 9.5, the starch paste after the adjusted pH value;
4) add urea in the starch paste after regulating the pH value, mixing obtains mixture A;
5) the mixture A that step 4) is obtained is warming up to 97 ℃, and insulation 2h is that the formic acid adjusting pH of 30wt%, 0.1ml is 8 with concentration then, obtains mixture B;
6) add formaldehyde in the mixture B that step 5) obtains, temperature is reduced to 95 ℃, and insulation 30min obtains mixture C;
7) mixture C that step 6) is obtained is cooled to 55 ℃, adds the 11.0ml dimethylamine, and reaction 4h obtains mixture D;
8) mixture D being neutralized to pH with hydrochloric acid is 7.0, obtains mixture E (thick product);
9) mixture E that step 8) is obtained precipitates with dehydrated alcohol, and the flush away small organic molecule has washing again, get comparatively purified product, dry (being dried to constant weight in 50 ℃ of vacuum drying ovens) pulverizes, and obtains cationization carbamate starch water conditioner (product).
With the cationization carbamate starch water conditioner (product) of starch and present embodiment respectively with pressing potassium bromide troche, do Infrared spectroscopy.Starch, urea and product infrared spectrogram are seen Fig. 1:
Starch is at 575.9cm
-1, 765.1cm
-1, 860.7cm
-1And 3396.0cm
-1Be characteristic peak-CH
2-and-wavelength of OH-correspondence.Urea is at 1682.6cm
-1There are acid amides characteristic peak, 3444.0cm in the place
-1And 3347.6cm
-1There is the stretching vibration peak of N-H at the place, and 1460.8cm
-1The characteristic absorbance at place.Cationization carbamate starch water conditioner (product) is at 3375.3cm
-1The place has-0H and-NH stretching vibration, at 858.3cm
-1There are couple methylene ether link characteristic absorbance and 1259.2cm in the place
-1The acid amides III bands of a spectrum that place's C-N-H vibration produces.
The result shows: urea and starch success grafting.
The flocculating effect experiment:
1) the bentonite suspension 100ml of preparation 0.5wt% concentration, totally 5 parts;
2) accurately take by weighing 0.200g cationization carbamate starch water conditioner (product), totally 4 parts;
3) under same stirring velocity, every interval 1min adds 1 part of cationization carbamate starch water conditioner in bentonite suspension, and churning time is the numbering 1 of 1min, the numbering 2 of 2min, the numbering 3 of 3min, the numbering 4 of 4min, 1min is stirred in contrast, numbering CK;
4) after stirring finishes, change over to simultaneously in the 100ml measuring bottle, leave standstill, every interval certain hour is taken pictures;
5) the relatively effect of water conditioner and the influence of churning time.
The flocculation figure of water conditioner sees Fig. 2: water conditioner just has tangible flocculating effect in the churning time of 1min, occurs significantly flocculating the interface when 2min, and the clarified liq volume has reached 80-82ml when 4min.The clarification volume is 82-83ml when 8min, and when 20min, the interface does not appear in contrast, and the clarification volume of handling is about 83.5ml.
Churning time is not obvious to the flocculating effect influence.
The result shows: cationization carbamate starch water conditioner has flocculating effect preferably.
Embodiment 2:
Prepare the method for cationization carbamate starch water conditioner, it comprises the steps:
1) choosing of raw material: press starch: urea: formaldehyde: the mol ratio of dimethylamine=1: 1: 1: 1, choose starch, urea, formaldehyde and dimethylamine, press water: the mass ratio of starch=9: 1, choose water, standby;
2) get starch and water stirs evenly, be warming up to 90 ℃, be incubated 5 minutes,, obtain starch paste starch pasting;
3) with NaOH aqueous solution regulating step 2) pH of the starch paste that obtains is 9.5, the starch paste after the adjusted pH value;
4) add urea in the starch paste after regulating the pH value, mixing obtains mixture A;
5) the mixture A that step 4) is obtained is warming up to 95 ℃, insulation 1h, and regulating pH with formic acid then is 8, obtains mixture B;
6) add formaldehyde in the mixture B that step 5) obtains, temperature is reduced to 90 ℃, and insulation 30min obtains mixture C;
7) mixture C that step 6) is obtained is cooled to 50 ℃, adds dimethylamine, and reaction 3h obtains mixture D;
8) mixture D being neutralized to pH with hydrochloric acid is 6.5, obtains mixture E;
9) the mixture E drying that step 8) is obtained obtains cationization carbamate starch water conditioner.
The flocculating effect experiment:
1) the bentonite suspension 100ml of preparation 0.5wt% concentration, totally 5 parts;
2) accurately take by weighing 0.200g cationization carbamate starch water conditioner (product), totally 4 parts;
3) under same stirring velocity, every interval 1min adds 1 part of cationization carbamate starch water conditioner in bentonite suspension, and churning time is the numbering 1 of 1min, the numbering 2 of 2min, the numbering 3 of 3min, the numbering 4 of 4min, 1min is stirred in contrast, numbering CK;
4) after stirring finishes, change over to simultaneously in the 100ml measuring bottle, leave standstill, every interval certain hour is taken pictures;
5) the relatively effect of flocculation agent and the influence of churning time.
Flocculation agent just has tangible flocculating effect in the churning time of 1min, occurs significantly flocculating the interface when 2min, and the clarified liq volume has reached 80-82ml when 4min.The clarification volume is 82-83ml when 8min, and when 20min, the interface does not appear in contrast, and the clarification volume of handling is at 83.5ml left side stone.
Churning time is not obvious to the flocculating effect influence.
The result shows: cationization carbamate starch water conditioner has flocculating effect preferably.
Embodiment 3:
Prepare the method for cationization carbamate starch water conditioner, it comprises the steps:
1) choosing of raw material: press starch: urea: formaldehyde: the mol ratio of dimethylamine=1: 1: 1: 1, choose starch, urea, formaldehyde and dimethylamine, press water: the mass ratio of starch=9: 1, choose water, standby;
2) get starch and water stirs evenly, be warming up to 90 ℃, be incubated 20 minutes,, obtain starch paste starch pasting;
3) with NaOH aqueous solution regulating step 2) pH of the starch paste that obtains is 11, the starch paste after the adjusted pH value;
4) add urea in the starch paste after regulating the pH value, mixing obtains mixture A;
5) the mixture A that step 4) is obtained is warming up to 97 ℃, insulation 2h, and regulating pH with formic acid or hydrochloric acid then is 9, obtains mixture B;
6) add formaldehyde in the mixture B that step 5) obtains, temperature is reduced to 95 ℃, and insulation 60min obtains mixture C;
7) mixture C that step 6) is obtained is cooled to 55 ℃, adds dimethylamine, and reaction 5h obtains mixture D;
8) mixture D being neutralized to pH with hydrochloric acid is 7.0, obtains mixture E;
9) the mixture E drying that step 8) is obtained obtains cationization carbamate starch water conditioner.
The flocculating effect experiment:
1) the bentonite suspension 100ml of preparation 0.5wt% concentration, totally 5 parts;
2) accurately take by weighing 0.200g cationization carbamate starch water conditioner (product), totally 4 parts;
3) under same stirring velocity, every interval 1min adds 1 part of cationization carbamate starch water conditioner in bentonite suspension, and churning time is the numbering 1 of 1min, the numbering 2 of 2min, the numbering 3 of 3min, the numbering 4 of 4min, 1min is stirred in contrast, numbering CK;
4) after stirring finishes, change over to simultaneously in the 100ml measuring bottle, leave standstill, every interval certain hour is taken pictures;
5) the relatively effect of flocculation agent and the influence of churning time.
Flocculation agent just has tangible flocculating effect in the churning time of 1min, occurs significantly flocculating the interface when 2min, and the clarified liq volume has reached 80-82ml when 4min.The clarification volume is 82-83ml when 8min, and when 20min, the interface does not appear in contrast, and the clarification volume of handling is about 83.5ml.
Churning time is not obvious to the flocculating effect influence.
The result shows: cationization carbamate starch water conditioner has flocculating effect preferably.
Claims (4)
1. the method for preparing cationization carbamate starch water conditioner is characterized in that it comprises the steps:
1) choosing of raw material: press starch: urea: formaldehyde: the mol ratio of dimethylamine=1: 1: 1: 1, choose starch, urea, formaldehyde and dimethylamine, press water: the mass ratio of starch=9: 1, choose water, standby;
2) get starch and water stirs evenly, be warming up to 90 ℃, be incubated 5-20 minute, obtain starch paste;
3) with NaOH aqueous solution regulating step 2) pH of the starch paste that obtains is 9.0-11, the starch paste after the adjusted pH value;
4) add urea in the starch paste after regulating the pH value, mixing obtains mixture A;
5) the mixture A that step 4) is obtained is warming up to 95-97 ℃, insulation 1-2h, and regulating pH with formic acid or hydrochloric acid then is 8-9, obtains mixture B;
6) add formaldehyde in the mixture B that step 5) obtains, temperature is reduced to 90-95 ℃, and insulation 30-60min obtains mixture C;
7) mixture C that step 6) is obtained is cooled to 50-55 ℃, adds dimethylamine, and reaction 3-5h obtains mixture D;
8) mixture D being neutralized to pH with hydrochloric acid is 6.5-7.0, obtains mixture E;
9) the mixture E drying that step 8) is obtained obtains cationization carbamate starch water conditioner.
2. the method for preparing cationization carbamate starch water conditioner according to claim 1 is characterized in that: the concentration of the described NaOH aqueous solution is 10-30wt%.
3. the method for preparing cationization carbamate starch water conditioner according to claim 1 is characterized in that: the concentration of described formic acid is 10-30wt%.
4. the method for preparing cationization carbamate starch water conditioner according to claim 1 is characterized in that: the concentration of described hydrochloric acid is 10-30wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333306A (en) * | 2013-07-16 | 2013-10-02 | 湖北省农业科学院农产品加工与核农技术研究所 | Preparation method of water-soluble polyurethane graft starch water treatment agent |
| CN108495821A (en) * | 2015-12-09 | 2018-09-04 | 高性能聚乙烯有限责任公司 | Composition for removing removing sulfate and metal from waste water and method |
| CN112439390A (en) * | 2020-10-30 | 2021-03-05 | 广西大学 | Magnetic aminated starch bentonite wastewater treatment agent and preparation method thereof |
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| CN1524801A (en) * | 2003-09-15 | 2004-09-01 | 武汉理工大学 | Coagulate method of water treatment purifying technology |
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| CN1257840A (en) * | 1998-12-22 | 2000-06-28 | 顺德市杏坛镇麦村恒业精细化工厂 | High-molecular cationic flocculant of starch graft acrylamide and its preparing process |
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| CN1644521A (en) * | 2004-12-30 | 2005-07-27 | 王元英 | Production of red iron stone built agent |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103333306A (en) * | 2013-07-16 | 2013-10-02 | 湖北省农业科学院农产品加工与核农技术研究所 | Preparation method of water-soluble polyurethane graft starch water treatment agent |
| CN103333306B (en) * | 2013-07-16 | 2015-02-18 | 湖北省农业科学院农产品加工与核农技术研究所 | Preparation method of water-soluble polyurethane graft starch water treatment agent |
| CN108495821A (en) * | 2015-12-09 | 2018-09-04 | 高性能聚乙烯有限责任公司 | Composition for removing removing sulfate and metal from waste water and method |
| EP3386923A4 (en) * | 2015-12-09 | 2019-09-04 | Integrity Bio-Chemicals, LLC | Compositions and methods for the removal of sulfates and metals from waste water |
| CN112439390A (en) * | 2020-10-30 | 2021-03-05 | 广西大学 | Magnetic aminated starch bentonite wastewater treatment agent and preparation method thereof |
| CN112439390B (en) * | 2020-10-30 | 2022-07-05 | 广西大学 | Magnetic aminated starch bentonite wastewater treatment agent and preparation method thereof |
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