CN109851019A - A kind of cationic modified starch flocculant and preparation method thereof - Google Patents
A kind of cationic modified starch flocculant and preparation method thereof Download PDFInfo
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- CN109851019A CN109851019A CN201910164593.8A CN201910164593A CN109851019A CN 109851019 A CN109851019 A CN 109851019A CN 201910164593 A CN201910164593 A CN 201910164593A CN 109851019 A CN109851019 A CN 109851019A
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Abstract
The present invention relates to a kind of cationic modified starch flocculant, the cationic modified starch flocculant is cationic modified starch flocculant ESt-g-PDMC, connects etherifying agent GTA and monomer DMC on starch backbone.The invention further relates to a kind of preparation methods of cationic modified starch flocculant, first with the chloro- 2- hydroxypropyl ammonium chloride (CTA) of 3- for raw material, 2,3 epoxypropyltrimethylchloride chloride (GTA) of synthesizing cationic etherifying agent.Using second alcohol and water as reaction solution, NaOH is catalyst, synthesis etherificate cationic starch ESt.Again using this etherification starch as raw material, continues to carry out graft copolymerization with vinyl monomer, further increase the degree of substitution and flocculating property of product.
Description
Technical field
The invention belongs to flocculant for sewage treatment technical field, in particular to a kind of cationic modified starch flocculant and
Preparation method.
Background technique
Flocculation technique is widely used in wastewater treatment process, and the quality of flocculating effect often determines the fortune of follow-up process
Row situation, final outflow water water quality and expense.Which kind of flocculant is selected, is had emphatically for improving effluent quality, reducing water producing cost
The effect wanted.Currently, inorganic polymer and Syn-Organic flocculants play always important work in sewage treatment
With.But traditional inorganic polymer flocculant (bodied ferric sulfate, aluminium polychloride) dosage is big, it is affected by environment big, and
The secondary pollution of subsequent initiation also restricts its development.Syn-Organic flocculants, such as strong cation polyacrylamide
(CPAM), the advantages that polyvinyl pyridine, although having dosage small, flocculation ability is strong, and generation dross is few, high-efficient, is difficult
Degradation, part also have toxic side effect, and waste residue moisture content is high, and generation sludge volume is huge, and price is relatively expensive.
In natural water body, most of colloid and suspended particulate have negative electrical charge, and cationic flocculant can produce it
Raw charge neutrality and compression double electric layer effect, make suspended particulate unstability rapid subsidence and generate flocculating effect, therefore, cationic wadding
Solidifying agent is the hot spot studied at present.On starch segment have great amount of hydroxy group, have stronger reactivity, can by etherificate,
The methods of oxidation, esterification and graft copolymerization carry out chemical modification, prepare non-ionic, cationic, anionic and both sexes
Starch flocculant.And starch itself or intermediate product are nontoxic to the human body, and raw material sources are abundant, and it is cheap, so such wadding
The development of solidifying agent is favored very much.
Liu Chang etc. is raw material with amylomaize, and NaOH is catalyst, 2,3 epoxypropyltrimethylchloride chlorides
(GTA) it is cationic etherifying agent, is prepared for high substituted degree cation high amylose starches.Reaction dissolvent uses dioxane and water,
60 DEG C of reaction temperature, reaction time 7h.Degree of substitution up to 1.27, for 0.7% bentonite solution when, light transmittance up to 90% with
On.For Ma Yafeng etc. with cornstarch and acrylamide (AM) for raw material, ammonium persulfate and sodium hydrogensulfite are initiator, are first synthesized
Starch/AM graft copolymer flocculant, then using GTA as cationic etherifying agent, to starch graft copolymer carried out sun from
Sonization.The flocculant is to the turbidity removal rate of coal mine wastewater water sample up to 95.6%.
Summary of the invention
The purpose of the present invention is to provide a kind of cationic modified starch flocculants (ESt-g-PDMC), and starch source is wide
General, cheap, nontoxic and pollution-free, cationic modified starch is biodegradable, and price is lower than commercial polyacrylamide class high score
Sub- flocculant；It is another object of the present invention to provide the preparation method of cationic modified starch flocculant, this method will form sediment
Powder combines with the etherification reaction of etherifying agent and starch with the graft reaction of vinyl monomer, and the cationic starch of synthesis has
The advantage that grafting rate is high, flocculating property is good, biodegradable.
For achieving the above object, the present invention adopts the following technical scheme that:
A kind of cationic modified starch flocculant, the cationic modified starch flocculant are cationic modified starch flocculant
ESt-g-PDMC connects etherifying agent GTA and monomer DMC on starch backbone.
A kind of preparation method of cationic modified starch flocculant, includes the following steps:
(1) equipped with thermometer, condenser pipe, blender and dropping funel four-hole boiling flask in, be added 30-50mL ethyl alcohol and go from
The volume ratio of sub- water, ethyl alcohol and deionized water is 2:1-1:1；
(2) 10g cornstarch is added, is heated to 65-80 DEG C, etherifying agent GTA0.05-0.07mol is added dropwise；
(3) it after dripping etherifying agent, then is added dropwise in catalyst n aOH solution 15-20mL, 30-40min and is added dropwise；
(4) isothermal reaction 3-5h；
(5) reaction system glacial acetic acid adjusts pH value to 7, and reaction temperature is reduced to 40-60 DEG C；
(6) lead to N into system20.5h, the oxygen in exclusion system；
(7) it uses 10-15mL nitric acid solution dissolution ammonium ceric nitrate 0.5-1.5g as initiator, is added drop-wise in system；
(8) after causing 5min, then grafted monomers DMC 0.06-0.09mol is slowly added dropwise into system, is added dropwise in 30-40min
It finishes；
(9) isothermal reaction 3-5h；
(10) product is light yellow viscous liquid, is washed with ethyl alcohol precipitating, filters, is dried in vacuo at 50 DEG C, obtains brown powder
End, as cationic modified starch flocculant ESt-g-PDMC.
Further, in the step (2) etherifying agent used GTA's the preparation method is as follows:
(1) 0.04-0.06mol NaOH solution is taken, the concentration of the NaOH solution is 10mol/L, is put into conical flask, is put into
Temperature is reduced to 10 DEG C or less in ice bath；
(2) 0.04-0.06mol CTA solution is added drop-wise in conical flask, the molar ratio of NaOH and CTA are 1:1；
(3) 10min is reacted under magnetic stirring to get etherifying agent GTA.
Further, the concentration of catalyst n aOH solution is 1mol/L in step (3).
Further, the temperature of isothermal reaction is 65-80 DEG C in step (4).
Further, N in step (6)2Intake be 0.1-1mol, uniformly ventilate.
Further, the concentration of nitric acid solution is 1mol/L in step (7).
Further, the temperature of the isothermal reaction in step (9) is 40-60 DEG C.
Further, the dosage of ethyl alcohol is 500-1000mL in the washing of ethyl alcohol precipitating in step (10)；Vacuum is dry at 50 DEG C
Dry vacuum degree is 0.08-01MPa.
Beneficial effects of the present invention:
The ESt-g-PDMC degree of substitution that the present invention obtains is high, and flocculating effect and commercially available highly cationic polyacrylamide flocculant are imitated
Fruit is suitable, but raw materials used extensive, and cheap, manufacturing cost is low.And product is biodegradable, can be used as a kind of high
Effect, environmentally friendly cationic flocculant use.
In the present invention, first with the chloro- 2- hydroxypropyl ammonium chloride (CTA) of 3- for raw material, 2,3 epoxy of synthesizing cationic etherifying agent
Hydroxypropyltrimonium chloride (GTA).Using second alcohol and water as reaction solution, NaOH is catalyst, synthesis etherificate cationic starch ESt.
Again using this etherification starch as raw material, continues to carry out graft copolymerization with vinyl monomer, further increase the degree of substitution of product
And flocculating property.
Detailed description of the invention
Fig. 1 is the cationic modified starch flocculant ESt-g-PDMC prepared and the raw material used in the embodiment of the present invention 1
The infrared spectrogram of cornstarch.
In attached drawing, (a) cornstarch；(b) ESt-g-PDMC.
Specific embodiment
Embodiment 1:
(1) in the four-hole boiling flask equipped with thermometer, condenser pipe, blender and dropping funel, 30mL ethyl alcohol and deionization is added
The volume ratio of water, ethyl alcohol and deionized water is 1:1.10g cornstarch is added, is heated to 70 DEG C, etherifying agent GTA is added dropwise
0.05mol.After dripping etherifying agent, then it is slowly added dropwise in catalyst n aOH solution (1mol/L) 20mL, 30min and is added dropwise.
The isothermal reaction 3h at 70 DEG C；
(2) reaction system glacial acetic acid adjusts pH value to neutrality, and reaction temperature is reduced to 40 DEG C.Lead to N2 0.5h into system,
Oxygen in exclusion system.It uses 15mL nitric acid solution (1mol/L) dissolution ammonium ceric nitrate 1.25g as initiator, is added drop-wise to system
In.After causing 5min, then grafted monomers DMC 0.06mol is slowly added dropwise into system, is added dropwise in 30min.40 DEG C of perseverances
Temperature reaction 4h.
Measuring product graft rate is 121.4%, and being applied to optimal addition dosage when 2% aqueous suspension ofkaolin is 5mg/L, and turbidity can
It is reduced to 33.46NTU.
The cationic modified starch flocculant ESt-g-PDMC prepared in the present invention and the raw material cornstarch used it is red
External spectrum as shown in Figure 1, as can be seen from Figure 1 ESt-g-PDMC other than keeping all characteristic absorption peak of ative starch,
1383cm-1There is an apparent absorption peak, which is c h bond symmetric curvature vibration absorption peak on quaternary ammonium salt group.
1480cm-1There is-N in place+(CH3) vibration absorption peak, can tentatively illustrate starch conversion reaction validity.In 1718cm-1There is absorption peak at place, this peak is the stretching vibration absworption peak of carbonyl C=O on side chain PDMC.It is demonstrated by the characteristic absorption peak in figure
Etherifying agent GTA and monomer DMC have been connected on starch backbone.
Embodiment 2:
(1) in the four-hole boiling flask equipped with thermometer, condenser pipe, blender and dropping funel, 30mL ethyl alcohol and deionization is added
The volume ratio of water, ethyl alcohol and deionized water is 1:1.10g cornstarch is added, is heated to 70 DEG C, etherifying agent GTA is added dropwise
0.06mol.After dripping etherifying agent, then it is slowly added dropwise in catalyst n aOH solution (1mol/L) 20mL, 30min and is added dropwise.
The isothermal reaction 3h at 70 DEG C；
(2) reaction system glacial acetic acid adjusts pH value to neutrality, and reaction temperature is reduced to 40 DEG C.Lead to N into system20.5h,
Oxygen in exclusion system.It uses 15mL nitric acid solution (1mol/L) dissolution ammonium ceric nitrate 1.0g as initiator, is added drop-wise to system
In.After causing 5min, then grafted monomers DMC 0.04mol is slowly added dropwise into system, is added dropwise in 30min.40 DEG C of perseverances
Temperature reaction 4h.
Measuring product graft rate is 117.7%, when optimal addition dosage is 5mg/L when applied to 2% aqueous suspension ofkaolin, turbidity
56.71NTU can be reduced to.
Embodiment 3:
(1) in the four-hole boiling flask equipped with thermometer, condenser pipe, blender and dropping funel, 50mL ethyl alcohol and deionization is added
The volume ratio of water, ethyl alcohol and deionized water is 1:1.10g cornstarch is added, is heated to 70 DEG C, etherifying agent GTA is added dropwise
0.06mol.After dripping etherifying agent, then it is slowly added dropwise in catalyst n aOH solution (1mol/L) 20mL, 30min and is added dropwise.
The isothermal reaction 3h at 70 DEG C；
(2) reaction system glacial acetic acid adjusts pH value to neutrality, and reaction temperature is reduced to 40 DEG C.Lead to N into system20.5h,
Oxygen in exclusion system.It uses 15mL nitric acid solution (1mol/L) dissolution ammonium ceric nitrate 1.25g as initiator, is added drop-wise to system
In.After causing 5min, then grafted monomers DMC 0.06mol is slowly added dropwise into system, is added dropwise in 30min.40 DEG C of perseverances
Temperature reaction 4h.
Measuring product graft rate is 104.6%, when optimal addition dosage is 8mg/L when applied to 2% aqueous suspension ofkaolin, turbidity
80.0NTU can be reduced to.
Embodiment 4:
(1) in the four-hole boiling flask equipped with thermometer, condenser pipe, blender and dropping funel, 50mL ethyl alcohol and deionization is added
The volume ratio of water, ethyl alcohol and deionized water is 1:1.10g cornstarch is added, is heated to 70 DEG C, etherifying agent GTA is added dropwise
0.06mol.After dripping etherifying agent, then it is slowly added dropwise in catalyst n aOH solution (1mol/L) 20mL, 30min and is added dropwise.
The isothermal reaction 3h at 70 DEG C；
(2) reaction system glacial acetic acid adjusts pH value to neutrality, and reaction temperature is reduced to 40 DEG C.Lead to N into system20.5h,
Oxygen in exclusion system.It uses 15mL nitric acid solution (1mol/L) dissolution ammonium ceric nitrate 1.25g as initiator, is added drop-wise to system
In.After causing 5min, then grafted monomers DMC 0.06mol is slowly added dropwise into system, is added dropwise in 30min.40 DEG C of perseverances
Temperature reaction 4h.
Measuring product graft rate is 120.2%, when optimal addition dosage is 5mg/L when applied to 2% aqueous suspension ofkaolin, turbidity
37.54NTU can be reduced to.
Claims (8)
1. a kind of cationic modified starch flocculant, which is characterized in that the cationic modified starch flocculant changes for cation
Property starch flocculant ESt-g-PDMC connects etherifying agent GTA and monomer DMC on starch backbone.
2. a kind of preparation method of cationic modified starch flocculant, which comprises the steps of:
(1) equipped with thermometer, condenser pipe, blender and dropping funel four-hole boiling flask in, be added 30-50mL ethyl alcohol and go from
The volume ratio of sub- water, ethyl alcohol and deionized water is 2:1-1:1；
(2) 10g cornstarch is added, is heated to 65-80 DEG C, etherifying agent GTA0.05-0.07mol is added dropwise；
(3) it after dripping etherifying agent, then is added dropwise in catalyst n aOH solution 15-20mL, 30-40min and is added dropwise；
(4) isothermal reaction 3-5h；
(5) reaction system glacial acetic acid adjusts pH value to 7, and reaction temperature is reduced to 40-60 DEG C；
(6) lead to N into system20.5h, the oxygen in exclusion system；
(7) it uses 10-15mL nitric acid solution dissolution ammonium ceric nitrate 0.5-1.5g as initiator, is added drop-wise in system；
(8) after causing 5min, then grafted monomers DMC 0.06-0.09mol is slowly added dropwise into system, is added dropwise in 30-40min
It finishes；
(9) isothermal reaction 3-5h；
(10) product is light yellow viscous liquid, is washed with ethyl alcohol precipitating, filters, is dried in vacuo at 50 DEG C, obtains brown powder
End, as cationic modified starch flocculant ESt-g-PDMC.
3. a kind of preparation method of cationic modified starch flocculant according to claim 2, which is characterized in that the step
Suddenly in (2) etherifying agent used GTA's the preparation method is as follows:
(1) 0.04-0.06mol NaOH solution is taken, the concentration of the NaOH solution is 10mol/L, is put into conical flask, is put into
Temperature is reduced to 10 DEG C or less in ice bath；
(2) 0.04-0.06mol CTA solution is added drop-wise in conical flask, the molar ratio of NaOH and CTA are 1:1；
(3) 10min is reacted under magnetic stirring to get etherifying agent GTA.
4. a kind of preparation method of cationic modified starch flocculant according to claim 2, which is characterized in that
The concentration of catalyst n aOH solution is 1mol/L in step (3).
5. a kind of preparation method of cationic modified starch flocculant according to claim 2, which is characterized in that step
(4) temperature of isothermal reaction is 65-80 DEG C in.
6. a kind of preparation method of cationic modified starch flocculant according to claim 2, which is characterized in that
The concentration of nitric acid solution is 1mol/L in step (7).
7. a kind of preparation method of cationic modified starch flocculant according to claim 2, which is characterized in that
The temperature of isothermal reaction in step (9) is 40-60 DEG C.
8. a kind of preparation method of cationic modified starch flocculant according to claim 2, which is characterized in that
The dosage of ethyl alcohol is 500-1000mL in the washing of ethyl alcohol precipitating in step (10)；Vacuum degree is dried in vacuo at 50 DEG C is
0.08-01MPa。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121711A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Preparation method of high-cation-degree starch flocculant |
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|---|---|---|---|---|
| CN102604116A (en) * | 2012-03-02 | 2012-07-25 | 武汉纺织大学 | Modified starch-chitosan copolymer flocculating agent and preparation method thereof |
| CN105645547A (en) * | 2016-01-13 | 2016-06-08 | 福建汉祥纺织科技有限公司 | Modified starch-chitosan copolymer flocculant and preparation method thereof |
| CN107474188A (en) * | 2017-08-04 | 2017-12-15 | 河北省科学院能源研究所 | A kind of cationic starch flocculant and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604116A (en) * | 2012-03-02 | 2012-07-25 | 武汉纺织大学 | Modified starch-chitosan copolymer flocculating agent and preparation method thereof |
| CN105645547A (en) * | 2016-01-13 | 2016-06-08 | 福建汉祥纺织科技有限公司 | Modified starch-chitosan copolymer flocculant and preparation method thereof |
| CN107474188A (en) * | 2017-08-04 | 2017-12-15 | 河北省科学院能源研究所 | A kind of cationic starch flocculant and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121711A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Preparation method of high-cation-degree starch flocculant |
| CN113121711B (en) * | 2019-12-31 | 2022-07-08 | 中国石油化工股份有限公司 | Preparation method of high-cation-degree starch flocculant |
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Application publication date: 20190607 |