CN102225801B - 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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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. 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 long-term application stage, as using various heavy as initiator in the flocculation agent preparation process, especially acrylamide flocculating agent, there is the secondary pollution problem in preparation and the flocculation process, therefore, developing green, High-efficient Water treatment agent are 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 the method preparation has preferably flocculating effect.
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, for subsequent use;
2) get starch and water stirs evenly, be warming up to 90 ℃, be incubated 5-20 minute, with starch pasting, 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 of regulating after the pH value, mixing obtains mixture A;
5) with step 4) the mixture A that obtains is warming up to 95-97 ℃, and then insulation 1-2h is 8-9 with formic acid or salt acid for adjusting pH, obtains mixture B;
6) to step 5) add formaldehyde among the mixture B that obtains, temperature is down to 90-95 ℃, and insulation 30-60min obtains mixture C;
7) with step 6) mixture C that obtains 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) with step 8) mixture E that obtains is dry, obtains cationization carbamate starch water conditioner.
Described starch: urea: formaldehyde: the mol ratio of dimethylamine=1: 1: 1: 1, this proportioning can improve the percentage of grafting of monomer 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 the method preparation has preferably flocculating effect, 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 the conglomerate sewage purification such as water treatment 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 that cationization carbamate starch water conditioner is to the flocculating effect figure of bentonite suspension.
Embodiment
In order to understand better the present invention, 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), for subsequent use;
2) in a four-hole round-bottomed flask that electric 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, with starch pasting, obtain starch paste;
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 of regulating after the pH value, mixing obtains mixture A;
5) with step 4) the mixture A that obtains is warming up to 97 ℃, and then insulation 2h is that the first acid for adjusting pH of 30wt%, 0.1ml is 8 with concentration, obtains mixture B;
6) to step 5) add formaldehyde among the mixture B that obtains, temperature is down to 95 ℃, and insulation 30min obtains mixture C;
7) with step 6) mixture C that obtains 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) with step 8) mixture E that obtains precipitates with dehydrated alcohol, and the flush away small organic molecule has washing again, get comparatively pure 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 that OH-is corresponding.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 of the C-N-H of place generation of vibration.
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) stir complete after, 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 impact of churning time.
The flocculation figure of water conditioner sees Fig. 2: water conditioner just has obvious 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 processing is about 83.5ml.
Churning time is not obvious on the flocculating effect impact.
The result shows: cationization carbamate starch water conditioner has preferably flocculating effect.
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, for subsequent use;
2) get starch and water stirs evenly, be warming up to 90 ℃, be incubated 5 minutes, with starch pasting, obtain starch paste;
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 of regulating after the pH value, mixing obtains mixture A;
5) with step 4) the mixture A that obtains is warming up to 95 ℃, and then insulation 1h is 8 with the first acid for adjusting pH, obtains mixture B;
6) to step 5) add formaldehyde among the mixture B that obtains, temperature is down to 90 ℃, and insulation 30min obtains mixture C;
7) with step 6) mixture C that obtains 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) with step 8) mixture E that obtains is dry, 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) stir complete after, 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 impact of churning time.
Flocculation agent just has obvious 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 processing is at the left stone of 83.5ml.
Churning time is not obvious on the flocculating effect impact.
The result shows: cationization carbamate starch water conditioner has preferably flocculating effect.
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, for subsequent use;
2) get starch and water stirs evenly, be warming up to 90 ℃, be incubated 20 minutes, with starch pasting, obtain starch paste;
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 of regulating after the pH value, mixing obtains mixture A;
5) with step 4) the mixture A that obtains is warming up to 97 ℃, and then insulation 2h is 9 with formic acid or salt acid for adjusting pH, obtains mixture B;
6) to step 5) add formaldehyde among the mixture B that obtains, temperature is down to 95 ℃, and insulation 60min obtains mixture C;
7) with step 6) mixture C that obtains 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) with step 8) mixture E that obtains is dry, 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) stir complete after, 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 impact of churning time.
Flocculation agent just has obvious 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 processing is about 83.5ml.
Churning time is not obvious on the flocculating effect impact.
The result shows: cationization carbamate starch water conditioner has preferably flocculating effect.
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, for subsequent use;
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 of regulating after the pH value, mixing obtains mixture A;
5) with step 4) the mixture A that obtains is warming up to 95-97 ℃, and then insulation 1-2h is 8-9 with formic acid or salt acid for adjusting pH, obtains mixture B;
6) to step 5) add formaldehyde among the mixture B that obtains, temperature is down to 90-95 ℃, and insulation 30-60min obtains mixture C;
7) with step 6) mixture C that obtains 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) with step 8) mixture E that obtains is dry, obtains cationization carbamate starch water conditioner.
2. the method for preparing cationization carbamate starch water conditioner according to claim 1, it 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, it 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, it is characterized in that: the concentration of described hydrochloric acid is 10-30wt%.
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| AU2016366302A1 (en) * | 2015-12-09 | 2018-04-26 | Integrity Bio-Chemicals, Llc | Compositions and methods for the removal of sulfates and metals from waste water |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1524801A (en) * | 2003-09-15 | 2004-09-01 | 武汉理工大学 | Coagulate method of water treatment purifying technology |
| CN1644521A (en) * | 2004-12-30 | 2005-07-27 | 王元英 | Production of red iron stone built agent |
| CN101250020A (en) * | 2008-03-26 | 2008-08-27 | 山东省科学院新材料研究所 | Preparation of special dehydrant for paper-making sludge and use thereof |
| CN101817912A (en) * | 2010-05-07 | 2010-09-01 | 福州大学 | Formula and preparation method of cationic polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1524801A (en) * | 2003-09-15 | 2004-09-01 | 武汉理工大学 | Coagulate method of water treatment purifying technology |
| CN1644521A (en) * | 2004-12-30 | 2005-07-27 | 王元英 | Production of red iron stone built agent |
| CN101250020A (en) * | 2008-03-26 | 2008-08-27 | 山东省科学院新材料研究所 | Preparation of special dehydrant for paper-making sludge and use thereof |
| CN101817912A (en) * | 2010-05-07 | 2010-09-01 | 福州大学 | Formula and preparation method of cationic polymer |
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