CN109987687A - A kind of compound coagulant and its preparation method and application - Google Patents
A kind of compound coagulant and its preparation method and application Download PDFInfo
- Publication number
- CN109987687A CN109987687A CN201811456214.4A CN201811456214A CN109987687A CN 109987687 A CN109987687 A CN 109987687A CN 201811456214 A CN201811456214 A CN 201811456214A CN 109987687 A CN109987687 A CN 109987687A
- Authority
- CN
- China
- Prior art keywords
- reaction
- chitosan
- sulfuric acid
- compound coagulant
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of compound coagulants and its preparation method and application, it is using chitosan as raw material, sulfuric acid esterification, necleophilic reaction are successively carried out to chitosan, obtain compound coagulant, sulfuric acid esterification step: N is dissolved the chitosan in, in dinethylformamide, chitosan solution is obtained；Chitosan solution and esterifying reagent are carried out sulfuric acid esterification to be after reaction cooled to room temperature reaction solution, the pH value of reaction solution is then adjusted to neutrality, obtains Sulfated chitosans；Nucleophilic reaction step: cationic gemini polymer and Sulfated chitosans are added in the round-bottomed flask equipped with methanol solution, compound coagulant is prepared in temperature rising reflux.Functional groups and the loose and porous structures such as compound coagulant of the invention hydroxyl rich in, amino, sulfate have extremely strong adsorption bridging ability, have good flocculation, coagulation, adsorptivity.
Description
Technical field
The present invention relates to a kind of coagulant, and in particular to a kind of compound coagulant and its preparation method and application.
Background technique
Chitosan is as a kind of natural polysaccharide, because it is with stability, adsorption bridging, biological degradability and safety, ring
Guarantor field has broad application prospects.Chitosan itself is water-soluble lower, and adsorptivity is poor, therefore, not plus modified chitosan
With certain application limitation.So far, most study is to carry out the chemistry such as acetylation, carboxy methylation to chitosan to repair
Decorations, making it dissolve property increase, and have a large amount of functional group, but Sulfation modification of chitosan data is few, and with it is positive from
Sub- Shuangzi polymer is very few in the research being modified to the chitosan after modification.
Summary of the invention
For overcome the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of compound coagulants, this is compound
Functional groups and the loose and porous structures such as coagulant hydroxyl rich in, amino, sulfate have extremely strong adsorption bridging energy
Power has good flocculation, coagulation, adsorptivity.
The second object of the present invention is to provide a kind of preparation method of compound coagulant, and the preparation method is with natural resources
The saccharide raw material source of the low ecological load of high-energy synthetic high efficiency, low cost passes through optimum synthesis step and the efficient catalysis of selection
Agent uses to be conducive to the conventional of carbohydrate, gradually substitutes the petrochemical industry class product big to the load of ecological environment.
The third object of the present invention is to provide a kind of application of compound coagulant.
An object of the present invention adopts the following technical scheme that realization:
A kind of compound coagulant, which is characterized in that it is characterized in that, it be using chitosan as raw material, to chitosan according to
Secondary progress sulfuric acid esterification, necleophilic reaction, obtain compound coagulant.
The second object of the present invention adopts the following technical scheme that realization:
A kind of preparation method of compound coagulant, which comprises the following steps:
Sulfuric acid esterification step: dissolving the chitosan in n,N-Dimethylformamide, obtains chitosan solution；By shell
Glycan solution and esterifying reagent carry out sulfuric acid esterification and are after reaction cooled to room temperature reaction solution, then adjust reaction
The pH value of liquid obtains Sulfated chitosans to neutrality；
Nucleophilic reaction step: in the three neck round bottom flask equipped with electric mixer and thermometer, 0.5-1.0moL is added
Tetramethylethylenediamine adds 200-300mL dehydrated alcohol as reaction dissolvent, stirs evenly, and adds 40g carbonic acid sodium powder
End stirs and is warming up to 70-80 DEG C, then the brominated alkanes of 0.5-1.2moL are added dropwise, and stirs when being added dropwise, after being added dropwise,
Under conditions of 80 DEG C of constant temperature, it is stirred to react 2-4h, after reaction, reaction solution is light yellow to get poly- to cationic gemini
Close object；Then cationic gemini polymer and Sulfated chitosans are added in the round-bottomed flask equipped with methanol solution, are risen
Temperature reflux 8h, is prepared compound coagulant.
Further, in sulfuric acid esterification step, esterifying reagent the preparation method is as follows: equipped with electric mixer and
Pyridine is added in the three neck round bottom flask of thermometer, is placed in cooling in salt water ice bath, chlorosulfonic acid is added dropwise under agitation,
The volume ratio of chlorosulfonic acid and pyridine is that 1:4-6 obtains esterifying reagent after reaction, spare.
Further, the preparation method of esterifying reagent needs to complete whole operation process in 40min.
Further, in sulfuric acid esterification step, the reaction temperature of sulfuric acid esterification is 50-90 DEG C.
Further, in sulfuric acid esterification step, the reaction time of sulfuric acid esterification is 2-5h.
Further, in sulfuric acid esterification step, the volume ratio of esterifying reagent and chitosan solution is 5-7:4.
Further, in sulfuric acid esterification step, after reaction, reaction solution is cooled to room temperature, 150mL is pre-chilled
Water be added reaction solution in, then with concentration be 20% NaOH solution adjust reaction solution pH value to neutrality, obtain sulfuric ester
Change chitosan.
Further, in nucleophilic reaction step, the molar ratio of cationic gemini polymer and Sulfated chitosans sulfuric acid
Example is 1.5-2.5:1.
Three achieved the object of the present invention can be reached by adopting the following technical scheme that:
The application of compound coagulant described in an object of the present invention: processing oily waste water or landfill leachate are used as
Coagulant.
The beneficial effects of the present invention are:
The mechanism of action of compound coagulant of the invention is mainly the charge neutrality effect of dication charge, uses spacer group
Two hydrophobic chains are connected, are prepared containing there are two the long-chain intermediate of reaction site, intermediate is anti-with carbohydrate derivative nucleophilic again
It answers, preparing tool, there are two the cationic gemini polymer of hydrophilic group.In view of three-dimensional effect, the reaction constrained by two sides long-chain
The activity in site decreases, therefore must react with there is more strongly active Sulfated chitosans, prepares the compound of greater activity
Coagulant, functional groups and the loose and porous structures such as compound coagulant hydroxyl rich in, amino, sulfate have extremely strong
Adsorption bridging ability, have good flocculation, coagulation, adsorptivity.Meanwhile compound coagulant selection is synthesized with natural resources
The saccharide raw material source of the low ecological load of high-energy and high-efficiency low cost, suitable synthetic method and efficient catalyst, to be conducive to
The conventional of carbohydrate uses, and gradually substitutes the petrochemical industry class product big to the load of ecological environment.
Detailed description of the invention
Fig. 1 is the comparison diagram that different coagulants sample influences oily waste water flocculating property；
In Fig. 1, A1 is the coagulant sample of embodiment 1, and A2 is the coagulant sample of embodiment 2, and A3 is the mixed of embodiment 3
Solidifying agent sample, A4 are the coagulant sample of embodiment 4；
Fig. 2 is the comparison diagram that different coagulants sample influences COD of waste leachate removal rate；
In Fig. 2, B1 is the coagulant sample of embodiment 1, and B2 is the coagulant sample of embodiment 2, and B3 is the mixed of embodiment 3
Solidifying agent sample, B4 are the coagulant sample of embodiment 4.
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
A kind of compound coagulant, it is successively to carry out sulfuric acid esterification, nucleophilic to chitosan using chitosan as raw material
Reaction, obtains compound coagulant.
Compound coagulant of the invention is a kind of cationic gemini polymer modification Sulfated chitosans compound coagulant,
Chitosan full name is Chitosan (1-4) -2 amino-beta-D glucose first, is unique cationic polysaccharide in nature, this
One characteristic allows chitosan and negatively charged polyanion to form polymer, and still, chitosan itself is water-soluble lower, inhales
Attached property is poor, therefore carries out the modified chitosan of Sulfation to chitosan, and short texture has a large amount of charge, and water solubility increases
Greatly；Secondly with spacer group connect two hydrophobic chains, prepare containing there are two reaction site long-chain intermediate, intermediate again with
Carbohydrate derivative necleophilic reaction, preparing tool, there are two the cationic gemini polymer of hydrophilic group.Glycosylation is adjustable
The space structure and hydrophilic-hydrophobic balance of cationic gemini polymer may be more advantageous to the polymer in the suction of oil-water interfaces
It is attached, there is good flocculation, coagulation, adsorptivity.
Cationic gemini polymer modification Sulfated chitosans compound coagulant be using the carbohydrate of natural reproducible as
Environmentally friendly " green " coagulant of raw material preparation.Such product is using glycosyl group as hydrophilic head base, with special more
Hydroxyl, sulfuric acid based structures, so that its surface-active be made to be significantly improved.In addition, also meet biological safety, biocompatibility
With " Green Chemistry " principle of biological degradability, had broad application prospects in environment protection field.
A kind of preparation method of compound coagulant, comprising the following steps:
Sulfuric acid esterification step: dissolving the chitosan in n,N-Dimethylformamide, obtains chitosan solution；By shell
Glycan solution and esterifying reagent carry out sulfuric acid esterification and are after reaction cooled to room temperature reaction solution, then adjust reaction
The pH value of liquid obtains Sulfated chitosans to neutrality；
Nucleophilic reaction step: in the three neck round bottom flask equipped with electric mixer and thermometer, 0.5-1.0moL is added
Tetramethylethylenediamine adds 200-300mL dehydrated alcohol as reaction dissolvent, stirs evenly, and adds 40g carbonic acid sodium powder
End stirs and is warming up to 70-80 DEG C, then the brominated alkanes of 0.5-1.2moL are added dropwise, and stirs when being added dropwise, after being added dropwise,
Under conditions of 80 DEG C of constant temperature, it is stirred to react 2-4h, after reaction, reaction solution is light yellow to get poly- to cationic gemini
Close object；Then cationic gemini polymer and Sulfated chitosans are added in the round-bottomed flask equipped with methanol solution, are risen
Temperature reflux 8h, is prepared compound coagulant.
As the mode that further carries out, in sulfuric acid esterification step, esterifying reagent the preparation method is as follows: being equipped with
Pyridine is added in the three neck round bottom flask of electric mixer and thermometer, be placed in salt water ice bath it is cooling, under agitation by
It is added dropwise to chlorosulfonic acid, the volume ratio of chlorosulfonic acid and pyridine is that 1:4-6 obtains esterifying reagent after reaction, spare.
As the mode that further carries out, the preparation method of esterifying reagent needs to complete whole operation process in 40min.
As the mode that further carries out, in sulfuric acid esterification step, the reaction temperature of sulfuric acid esterification is 50-90
℃。
As the mode that further carries out, in sulfuric acid esterification step, the reaction time of sulfuric acid esterification is 2-5h.
As the mode that further carries out, in sulfuric acid esterification step, the volume ratio of esterifying reagent and chitosan solution
For 5-7:4.
As the mode that further carries out, in sulfuric acid esterification step, after reaction, reaction solution is cooled to room
The water of 150mL pre-cooling is added in reaction solution temperature, and the NaOH solution for being then 20% with concentration adjusts the pH value of reaction solution into
Property, obtain Sulfated chitosans.
As the mode that further carries out, in nucleophilic reaction step, cationic gemini polymer and Sulfated chitosans
The molar ratio of sulfuric acid is 1.5-2.5:1.
As the mode that further carries out, in nucleophilic reaction step, brominated alkanes are bromododecane or bromotetradecane.
The application of the compound coagulant: it is used as the coagulant of processing oily waste water or landfill leachate.
It is specific embodiment of the present invention below, used raw material, equipment etc. remove special limit in the following embodiments
It can be obtained by buying pattern outside fixed.
Embodiment 1:
A kind of preparation method of compound coagulant, comprising the following steps:
1) sulfuric acid esterification step:
1-1) in the three neck round bottom flask equipped with electric mixer and thermometer, 250mL flask is added in 10ml pyridine
In, it is placed in salt water ice bath cooling, is added dropwise chlorosulfonic acid under agitation, the volume ratio of chlorosulfonic acid and pyridine is 1:6, instead
After answering, esterifying reagent is obtained, it is spare；Whole operation process is completed in 40min；
It 1-2) dissolves the chitosan in the n,N-Dimethylformamide of 40mL, obtains chitosan solution；Chitosan is molten
The volume ratio of liquid and esterifying reagent progress sulfuric acid esterification, esterifying reagent and chitosan solution is 6:4, reaction temperature 50
DEG C, reaction solution is cooled to room temperature by reaction time 3h after reaction, the water of 150mL pre-cooling is added in reaction solution, so
The NaOH solution for being afterwards 20% with concentration adjusts the pH value of reaction solution to neutrality, obtains Sulfated chitosans；
2) nucleophilic reaction step:
2-1) in the three neck round bottom flask equipped with electric mixer and thermometer, 0.5moL tetramethylethylenediamine is added,
200mL dehydrated alcohol is added as reaction dissolvent, is stirred evenly, 40g powdered sodium carbonate is added, stirs and is warming up to 70
DEG C, then the brominated alkanes of 0.6moL are added dropwise, it is stirred when being added dropwise, after being added dropwise, under conditions of 80 DEG C of constant temperature, stirring is anti-
Answer 3h, after reaction, reaction solution be it is light yellow to get arrive cationic gemini polymer；
2-2) then 1.5moL cationic gemini polymer and 1.0moL Sulfated chitosans are added to equipped with methanol
In the round-bottomed flask of solution, compound coagulant is prepared in temperature rising reflux 8h.
Embodiment 2:
A kind of preparation method of compound coagulant, comprising the following steps:
1) sulfuric acid esterification step:
1-1) in the three neck round bottom flask equipped with electric mixer and thermometer, 250mL flask is added in 10ml pyridine
In, it is placed in salt water ice bath cooling, is added dropwise chlorosulfonic acid under agitation, the volume ratio of chlorosulfonic acid and pyridine is 1:4, instead
After answering, esterifying reagent is obtained, it is spare；Whole operation process is completed in 40min；
It 1-2) dissolves the chitosan in the n,N-Dimethylformamide of 40mL, obtains chitosan solution；Chitosan is molten
The volume ratio of liquid and esterifying reagent progress sulfuric acid esterification, esterifying reagent and chitosan solution is 5:4, reaction temperature 50
DEG C, reaction solution is cooled to room temperature by reaction time 2h after reaction, the water of 150mL pre-cooling is added in reaction solution, so
The NaOH solution for being afterwards 20% with concentration adjusts the pH value of reaction solution to neutrality, obtains Sulfated chitosans；
2) nucleophilic reaction step:
2-1) in the three neck round bottom flask equipped with electric mixer and thermometer, 1.0moL tetramethylethylenediamine is added,
250mL dehydrated alcohol is added as reaction dissolvent, is stirred evenly, 40g powdered sodium carbonate is added, stirs and is warming up to 70
DEG C, then the brominated alkanes of 1.2moL are added dropwise, it is stirred when being added dropwise, after being added dropwise, under conditions of 80 DEG C of constant temperature, stirring is anti-
Answer 2h, after reaction, reaction solution be it is light yellow to get arrive cationic gemini polymer；
2-2) then 2.0moL cationic gemini polymer and 1.0moL Sulfated chitosans are added to equipped with methanol
In the round-bottomed flask of solution, compound coagulant is prepared in temperature rising reflux 8h.
Embodiment 3:
A kind of preparation method of compound coagulant, comprising the following steps:
1) sulfuric acid esterification step:
1-1) in the three neck round bottom flask equipped with electric mixer and thermometer, 250mL flask is added in 10ml pyridine
In, it is placed in salt water ice bath cooling, is added dropwise chlorosulfonic acid under agitation, the volume ratio of chlorosulfonic acid and pyridine is 1:5, instead
After answering, esterifying reagent is obtained, it is spare；Whole operation process is completed in 40min；
It 1-2) dissolves the chitosan in the n,N-Dimethylformamide of 40mL, obtains chitosan solution；Chitosan is molten
The volume ratio of liquid and esterifying reagent progress sulfuric acid esterification, esterifying reagent and chitosan solution is 7:4, reaction temperature 80
DEG C, reaction solution is cooled to room temperature by reaction time 5h after reaction, the water of 150mL pre-cooling is added in reaction solution, so
The NaOH solution for being afterwards 20% with concentration adjusts the pH value of reaction solution to neutrality, obtains Sulfated chitosans；
2) nucleophilic reaction step:
2-1) in the three neck round bottom flask equipped with electric mixer and thermometer, 0.8moL tetramethylethylenediamine is added,
300mL dehydrated alcohol is added as reaction dissolvent, is stirred evenly, 40g powdered sodium carbonate is added, stirs and is warming up to 70
DEG C, then the brominated alkanes of 1.0moL are added dropwise, it is stirred when being added dropwise, after being added dropwise, under conditions of 80 DEG C of constant temperature, stirring is anti-
Answer 3h, after reaction, reaction solution be it is light yellow to get arrive cationic gemini polymer；
2-2) then 2.5moL cationic gemini polymer and 1.0moL Sulfated chitosans are added to equipped with methanol
In the round-bottomed flask of solution, compound coagulant is prepared in temperature rising reflux 8h.
Embodiment 4:
A kind of preparation method of compound coagulant, comprising the following steps:
1) sulfuric acid esterification step:
1-1) in the three neck round bottom flask equipped with electric mixer and thermometer, 250mL flask is added in 10ml pyridine
In, it is placed in salt water ice bath cooling, is added dropwise chlorosulfonic acid under agitation, the volume ratio of chlorosulfonic acid and pyridine is 1:5, instead
After answering, esterifying reagent is obtained, it is spare；Whole operation process is completed in 40min；
It 1-2) dissolves the chitosan in the n,N-Dimethylformamide of 40mL, obtains chitosan solution；Chitosan is molten
The volume ratio of liquid and esterifying reagent progress sulfuric acid esterification, esterifying reagent and chitosan solution is 6.5:4, reaction temperature 90
DEG C, reaction solution is cooled to room temperature by reaction time 4h after reaction, the water of 150mL pre-cooling is added in reaction solution, so
The NaOH solution for being afterwards 20% with concentration adjusts the pH value of reaction solution to neutrality, obtains Sulfated chitosans；
2) nucleophilic reaction step:
2-1) in the three neck round bottom flask equipped with electric mixer and thermometer, 0.5moL tetramethylethylenediamine is added,
250mL dehydrated alcohol is added as reaction dissolvent, is stirred evenly, 40g powdered sodium carbonate is added, stirs and is warming up to 70
DEG C, then the brominated alkanes of 0.5moL are added dropwise, it is stirred when being added dropwise, after being added dropwise, under conditions of 80 DEG C of constant temperature, stirring is anti-
Answer 4h, after reaction, reaction solution be it is light yellow to get arrive cationic gemini polymer；
2-2) then 1.8moL cationic gemini polymer and 1.0moL Sulfated chitosans are added to equipped with methanol
In the round-bottomed flask of solution, compound coagulant is prepared in temperature rising reflux 8h.
Compliance test result:
In order to investigate influence of the different coagulants sample to coagulation effect, under certain condition (room temperature), according to different throwings
Dosage, measurement are calculated oil removal rate and are commented coagulation effect using the oil content of the waste water water sample before and after different sample treatments
Valence.
As seen from Figure 1, with the increase of sample dosage, the deoiling effect of oily waste water is consequently increased；It is low
Under dosage, oil removal rate increase is more rapid, and after dosage increases to 30mg/L, oil removal rate reaches maximum, flocculant usage
It continues growing, increase more gentle and is finally reached stabilization, oil removal rate increases unobvious.This may be with polymer cation group
Electrical neutralization and Shuangzi group the removal of oil is carried out to the binding ability of oil droplet, be conducive to improve deoiling effect.
Under certain condition, four kinds of coagulant samples have carried out coagulation experiment, every kind of coagulant volume point to landfill leachate
Number is respectively 0.02%, 0.04%, 0.06%, 0.08%, 0.1%5 series, measurement COD removal rate (%) that treated.
As seen from Figure 2, four kinds of coagulant sample volume scores are substantially at 0.04%, and COD removal rate highest, this can
Access and open riverfront can be provided because of sulfate group and cationic gemini group due to polymer, increase suction of the polymer to organic matter
Attached ability；When volume fraction increases, COD removal rate occurs lower by this may be due to the solubilization when volume fraction increases
Reinforce, colloidal solid electrical property reversion can be caused, generates protection and reduce coagulation.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of compound coagulant, which is characterized in that it is successively to carry out Sulfation to chitosan using chitosan as raw material
Reaction, necleophilic reaction, obtain compound coagulant.
2. a kind of preparation method of compound coagulant as described in claim 1, which comprises the following steps:
Sulfuric acid esterification step: dissolving the chitosan in n,N-Dimethylformamide, obtains chitosan solution；By chitosan
Solution and esterifying reagent carry out sulfuric acid esterification and are after reaction cooled to room temperature reaction solution, then adjust reaction solution
PH value obtains Sulfated chitosans to neutrality；
Nucleophilic reaction step: in the three neck round bottom flask equipped with electric mixer and thermometer, 0.5-1.0moL tetramethyl is added
Base ethylenediamine adds 200-300mL dehydrated alcohol as reaction dissolvent, stirs evenly, adds 40g powdered sodium carbonate, stir
It mixes and is warming up to 70-80 DEG C, then the brominated alkanes of 0.5-1.2moL are added dropwise, stirred when being added dropwise, after being added dropwise, in constant temperature
Under conditions of 80 DEG C, be stirred to react 2-4h, after reaction, reaction solution be it is light yellow to get arrive cationic gemini polymer；So
Cationic gemini polymer and Sulfated chitosans are added in the round-bottomed flask equipped with methanol solution afterwards, temperature rising reflux
Compound coagulant is prepared in 8h.
3. the preparation method of compound coagulant as claimed in claim 2, which is characterized in that in sulfuric acid esterification step, ester
Change reagent the preparation method is as follows: is added pyridine in the three neck round bottom flask equipped with electric mixer and thermometer, is placed in salt
It is cooling in water-ice bath, it is added dropwise chlorosulfonic acid under agitation, the volume ratio of chlorosulfonic acid and pyridine is 1:4-6, and reaction terminates
Afterwards, esterifying reagent is obtained, it is spare.
4. the preparation method of compound coagulant as claimed in claim 3, which is characterized in that the preparation method of esterifying reagent needs
Whole operation process is completed in 40min.
5. the preparation method of compound coagulant as claimed in claim 2, which is characterized in that in sulfuric acid esterification step, sulphur
The reaction temperature of Esterification reaction is 50-90 DEG C.
6. the preparation method of compound coagulant as claimed in claim 2, which is characterized in that in sulfuric acid esterification step, sulphur
The reaction time of Esterification reaction is 2-5h.
7. the preparation method of compound coagulant as claimed in claim 2, which is characterized in that in sulfuric acid esterification step, ester
The volume ratio for changing reagent and chitosan solution is 5-7:4.
8. the preparation method of compound coagulant as claimed in claim 2, which is characterized in that in sulfuric acid esterification step, instead
After answering, reaction solution is cooled to room temperature, the water of 150mL pre-cooling is added in reaction solution, is then 20% with concentration
NaOH solution adjusts the pH value of reaction solution to neutrality, obtains Sulfated chitosans.
9. the preparation method of compound coagulant as claimed in claim 2, which is characterized in that in nucleophilic reaction step, cation
The molar ratio of Shuangzi polymer and Sulfated chitosans sulfuric acid is 1.5-2.5:1.
10. a kind of application of compound coagulant as described in claim 1, it is characterised in that: be used as processing oily waste water
Or the coagulant of landfill leachate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811456214.4A CN109987687B (en) | 2018-11-30 | 2018-11-30 | Composite coagulant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811456214.4A CN109987687B (en) | 2018-11-30 | 2018-11-30 | Composite coagulant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109987687A true CN109987687A (en) | 2019-07-09 |
| CN109987687B CN109987687B (en) | 2022-09-06 |
Family
ID=67128686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811456214.4A Active CN109987687B (en) | 2018-11-30 | 2018-11-30 | Composite coagulant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109987687B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4976952A (en) * | 1987-05-09 | 1990-12-11 | Wella Aktiengesellschaft | Macromolecular, surface-active, quaternary, N-substituted chitosan derivatives as well as cosmetic composition based on these new chitosan derivatives |
| KR20100061987A (en) * | 2008-12-01 | 2010-06-10 | 한밭대학교 산학협력단 | The coagulation composition which contains chitosan and sulfate compounds for water treatment and a method of preparing thereof |
| CN101798133A (en) * | 2010-02-10 | 2010-08-11 | 湖北大学 | Composite algicide consisting of gemini surfactant and clay, and algae removal method |
| CN103012619A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
| CN104528863A (en) * | 2014-12-09 | 2015-04-22 | 厦门理工学院 | Method for removing heavy metals in garbage percolate through surfactant-modified attapulgite |
| CN108654703A (en) * | 2017-03-31 | 2018-10-16 | 南京理工大学 | A kind of preparation method of Gemini surface active agent pillared modification montmorillonite |
| CN108651462A (en) * | 2017-03-27 | 2018-10-16 | 中国石油化工股份有限公司 | Chitosan amphoteric ion fungicide and the preparation method and application thereof |
-
2018
- 2018-11-30 CN CN201811456214.4A patent/CN109987687B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4976952A (en) * | 1987-05-09 | 1990-12-11 | Wella Aktiengesellschaft | Macromolecular, surface-active, quaternary, N-substituted chitosan derivatives as well as cosmetic composition based on these new chitosan derivatives |
| KR20100061987A (en) * | 2008-12-01 | 2010-06-10 | 한밭대학교 산학협력단 | The coagulation composition which contains chitosan and sulfate compounds for water treatment and a method of preparing thereof |
| CN101798133A (en) * | 2010-02-10 | 2010-08-11 | 湖北大学 | Composite algicide consisting of gemini surfactant and clay, and algae removal method |
| CN103012619A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
| CN104528863A (en) * | 2014-12-09 | 2015-04-22 | 厦门理工学院 | Method for removing heavy metals in garbage percolate through surfactant-modified attapulgite |
| CN108651462A (en) * | 2017-03-27 | 2018-10-16 | 中国石油化工股份有限公司 | Chitosan amphoteric ion fungicide and the preparation method and application thereof |
| CN108654703A (en) * | 2017-03-31 | 2018-10-16 | 南京理工大学 | A kind of preparation method of Gemini surface active agent pillared modification montmorillonite |
Non-Patent Citations (3)
| Title |
|---|
| 段久芳: "《天然高分子材料》", 30 September 2016, 华中科技大学出版社 * |
| 范宇: "季铵盐Gemini表面活性剂/壳聚糖复合水凝胶的制备及吸附性能研究", 《中国优秀硕士学位论文 工程科技Ⅰ辑》 * |
| 许明标等: "《聚合物在油气田开采中的应用》", 31 January 2010, 中国地质大学出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109987687B (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104558323B (en) | A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof | |
| CN104971694B (en) | Inorganic-organic composite bentonite material and preparation method and application thereof | |
| CN103509199B (en) | Swelling particulate of polymer for drilling fluid and preparation method thereof | |
| CN104437676B (en) | Sulfonic acid type strong-acidity cation exchange resin and preparation method thereof | |
| CN106947025A (en) | A kind of preparation method based on starch graft acrylic acid and the compound water-keeping gel of sodium alginate, slag | |
| CN102304067A (en) | Method for preparing gydroxysulfobetaine amphoteric surface active agent including polyether chain segment | |
| CN109553701A (en) | A kind of preparation method of modification of chitosan polymer | |
| CN103113508B (en) | Super absorbent resin with lower liquid absorbing rate, and preparation method and application thereof | |
| CN102051332A (en) | Collection method of oil-containing microalgae | |
| CN104292387A (en) | Preparation method of high temperature resistant salt-resistant filtrate reducer | |
| CN104386700B (en) | A kind of method of preparing mesoporous silicon dioxide micro-sphere | |
| CN105330334A (en) | Preparation method of silane modified concrete internal curing agent | |
| CN105565459B (en) | A kind of poly-ferric chloride-paper mill sludge base aminated polymer composite flocculation agent and preparation method thereof | |
| CN103318995B (en) | Method for improving industrial waste alkali residue slurry flocculation effect | |
| CN113372516B (en) | Thickener ultrafine powder, giant arm type thickener, preparation method and application thereof | |
| CN103224569A (en) | Large-molecular hydrophobic anhydride modified starch and preparation method thereof | |
| CN109987687A (en) | A kind of compound coagulant and its preparation method and application | |
| CN102443177A (en) | Method for preparing amphoteric chitosan water reducing agents | |
| CN108217892A (en) | A kind of preparation method of cellulose-chitosan green flocculation material for the processing fabric dyeing waste water of multicomponent containing silk | |
| CN107352629A (en) | A kind of preparation method of Inorganic/organic Complex Flocculent | |
| CN107088386B (en) | A kind of Long carbon chain carboxylate surface active agent of high-dissolvability and its viscoelastic solution of formation | |
| CN109536157A (en) | Material and its slippery water, the multiplexing fracturing fluid of adjustable function are used for energy development | |
| CN103059223A (en) | Method for synthesizing super absorbent resin through graft copolymerization of alpha-potato starch | |
| CN109433099A (en) | A kind of preparation method and applications of lignin-base sodium alcohol ether carboxylate | |
| CN110746636B (en) | Temperature-sensitive sodium alginate/cellulose ether composite hydrogel and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |