CN106633046A - Synthesis method of cation modified gamma-polyglutamic acid and application thereof - Google Patents
Synthesis method of cation modified gamma-polyglutamic acid and application thereof Download PDFInfo
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- CN106633046A CN106633046A CN201710052764.9A CN201710052764A CN106633046A CN 106633046 A CN106633046 A CN 106633046A CN 201710052764 A CN201710052764 A CN 201710052764A CN 106633046 A CN106633046 A CN 106633046A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- 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
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Abstract
The invention relates to a synthesis method of cation modified gamma-polyglutamic acid and application thereof. The method comprises the following steps that (1) gamma-polyglutamic acid is added into a reaction kettle filled with distilled water; stirring is performed; (2) an etherifying agent of 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride and NaOH are respectively dissolved into water to respectively obtain an etherifying agent solution and alkali liquor; a gamma-polyglutamic acid water solution in the step (1) is subjected to swelling; then, the etherifying agent solution is dripped, and then the NaOH solution is dripped; cooling, precipitation, refrigeration and drying are performed; finally, a cation modified gamma-polyglutamic acid flocculant is obtained. The prepared cation modified gamma-polyglutamic acid has an obvious flocculating settling effect on seawater; the turbidity removal rate being 89 percent or higher can be reached when the dosing quantity is 2mg/L; the cation modified gamma-polyglutamic acid is an environmental-friendly flocculant.
Description
Technical field
The present invention relates to water-treatment technology field, and in particular to prepare a kind of cationic flocculant preparation method and
Its flocculating effect research in the seawater.
Background technology
With the continuous growth and the continuous development of modern industrialization of world population, the mankind are to the demand of water resource continuous
Growth, along with the unreasonable exploitation to freshwater resources and the continuous destruction to ecological environment, make the countries and regions of many
Occur in that water shortage problem in varying degrees.In order to solve the deficient problem of land freshwater resources and chemical mineral resources, each
Countries and regions are all in active development desalination technology and direct seawater utilization technology.But, the composition of seawater is more complicated,
Containing pollutants such as substantial amounts of suspended particulates, bulky grain organic matter, bacteriums in particularly inshore seawater, these pollutants are such as
Fruit is entered in STP, can be blocked and the production equipment such as corrosion pipeline or film, causes more serious economic loss.
So, must be further processed before using seawater.Flocculation sedimentation is a kind of seawater cleaning for generally adopting at present
The method of pretreatment.
Flocculant is a kind of colloid made in the aqueous solution or suspension de- surely generation floccule or flocky precipitate
Medicament.Flocculant can be divided into inorganic flocculating agent and the big class of organic flocculant two according to its chemical composition.Inorganic flocculating agent can be with
It is divided into inorganic polymer flocculant and inorganic flocculant；Organic flocculant can be divided into natural organic high-molecular flocculant, have again
Machine high polymer coagulant and microbial flocculant.The species of flocculant is very more, from single type to it is compound, from low molecule to height
Molecule, generally speaking the developing direction of flocculant is non-toxic efficient, cheap practicality.The low price of inorganic flocculating agent, but use
Amount is larger, some are harmful to ecological environment and human health；Organic polymer coargulator consumption is few, flocculating effect strong, but often
The residual monomer of acrylic amide high polymer has rugged, the carcinogenic, mutagenicity of cause, makes the use of organic polymer coargulator
Scope is limited by larger.Microbial flocculant is a kind of nontoxic biological polymeric compound, including functional polysaccharide and
Functional protein substance, be by the use of the cell membrane of microorganism metabolite or microbial cell as flocculant.It is external
Commercially producing for microbial flocculant starts from the nineties in 20th century, because which overcoming secondary pollution and harmful etc. lacking
Point, so being with a wide range of applications.
Gamma-polyglutamic acid is a kind of novel green biomaterial of water-soluble biodegradable, with edibility, film forming
Property, nontoxicity, moisture retention, caking property the features such as, its in terms of water process have vast potential for future development.Cation-modified
Gamma-polyglutamic acid belongs to microbial flocculant, and it not only has the advantages that usual microbial flocculant, and big because existing in seawater
The Ca of amount2+, increased its flocculating effect in the seawater so as to more adapt to seawer system.
The content of the invention
The purpose of the present invention is the deficiency for current techniques, there is provided a kind of cation-modified gamma-polyglutamic acid flocculating agent
Method.The method 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (etherifying agent) are come the gamma-polyglutamic acid that is modified.It is modified with it
Gamma-polyglutamic acid carry positive charge, and the suspension in seawater mainly carries negative electrical charge, so cation-modified γ-
Polyglutamic acid is particularly well-suited to contain Ca in seawer system, and system2+Can with the flocculating setting of promotion system suspension, and because
To contain substantial amounts of Ca in seawater2+, so the gamma-polyglutamic acid after cation-modified is more suitable for the flocculation of seawater.
The technical scheme is that：
A kind of synthetic method of cation-modified gamma-polyglutamic acid flocculating agent, comprises the steps of
1), gamma-polyglutamic acid is added in the reactor equipped with distilled water, stirring；Wherein, 50～100ml distilled water adds 1
～10g gamma-polyglutamic acids；
2), etherifying agent and alkali are dissolved into respectively in water, etherificate agent solution and alkali lye is respectively obtained；
Wherein, mol ratio etherifying agent：Alkali=1：1～1.3；Described etherifying agent is the chloro- 2- Hydroxyproyl Trimethyls chlorinations of 3-
Ammonium；Described alkali is NaOH；
3), by step 1) in the gamma-polyglutamic acid aqueous solution be heated to 30 DEG C -70 DEG C, then swelling 1h instills step 2)
In etherificate agent solution, be added dropwise alkali lye after 5min again, react 3-7h, obtain mixed solution；
Wherein, volume ratio gamma-polyglutamic acid solution：Alkali lye：Etherificate agent solution=1：1～1.3：0.3～2；
4), mixed liquor is naturally cooled into room temperature, adds the ethanol precipitation of 3～5 times of mixed liquor volume amounts, 4 DEG C of degree
Lower refrigeration 12 hours.
5), the solution after refrigeration is filtered, precipitation washed with ethanol, be then dried, finally obtain it is cation-modified after
Gamma-polyglutamic acid flocculating agent powder；
Described etherificate agent solution obtains concentration and is preferably mass ratio 60～65%.The concentration of described alkali lye is preferably 1.3
～9.1mol/L.
The application process of described cation-modified gamma-polyglutamic acid flocculating agent, for the seawater flocculation of high concentrtion.
The application process of described cation-modified gamma-polyglutamic acid flocculating agent, specifically includes following steps：
Described cation-modified gamma-polyglutamic acid solution is added in high-turbidity seawater, then 500～700r/min is stirred
2～3min is mixed, then 4～6min is stirred under 200～300r/min, stood, complete flocculation；
Wherein, the turbidity of high-turbidity seawater be 60～120NTU, cation-modified gamma-polyglutamic acid solution be 0.005～
0.03g/100mL；Volume ratio high-turbidity seawater：Cation-modified gamma-polyglutamic acid solution=100:1～3.
Beneficial effects of the present invention are：
Cation-modified gamma-polyglutamic acid prepared by the present invention has obvious flocculating setting to act on to seawater, due to sea
Contain substantial amounts of Ca in water2+, and Ca2+Having to cation-modified gamma-polyglutamic acid significantly promote flocculating setting effect, institute
With the especially suitable seawer system of cation-modified gamma-polyglutamic acid of the present invention.(the gamma-polyglutamic acid wadding after cation-modified
The flocculation system of the particularly suitable high concentrtion of solidifying agent, goes turbidity to reach more than 89%.Now the flocculant of industrial application is main
It is inorganic flocculating agent and organic polymer coargulator, the dosage of inorganic flocculating agent and organic polymer coargulator in flocculation exists
More than tens milligrams per liter, and inorganic flocculating agent and organic polymer coargulator can produce when in use secondary pollution, to ring
Border produces pollution.And it is cation-modified after gamma-polyglutamic acid flocculating agent belong to microbial flocculant, and dosage in 2mg/
L can just reach more than 89% and go turbid rate, be environmentally friendly flocculant, using the γ-polyglutamic after cation-modified
Sour flocculant will not produce any pollution to environment)
Specific embodiment
Cation-modified gamma-polyglutamic acid synthesized by the present invention is applied to seawater flocculation, and seawater flocculation effect is by sea
The turbidity of water is measured the turbidity of seawater by nephelometer evaluating.
Described gamma-polyglutamic acid is commercially available well known materials.
Go the computing formula of turbid rate：Q=(Y1-Y2)/Y1, wherein Q is to remove turbid rate (%), Y1For former turbidity of sea water (NTU), Y2
For the turbidity of sea water (NTU) after flocculating setting.
Embodiment 1
There is nucleophilic substitution using gamma-polyglutamic acid and 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, NaOH is catalysis
Agent, aqueous phase reactions.
Synthesizing cationic is modified gamma-polyglutamic acid
Weighing 1g gamma-polyglutamic acids adds 10ml distilled water to be placed in the round-bottomed flask of 250ml, stirs.
(3- containing 0.07mol is chloro- to weigh 20.26g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution (65% aqueous solution)
2- hydroxypropyl-trimethyl ammonium chlorides) beaker is placed in, it is standby.
Weigh 0.091mol (3.64g) NaOH add 10ml it is water-soluble in beaker.It is standby.
The round-bottomed flask for being dissolved in the gamma-polyglutamic acid aqueous solution is fixed in heat collecting type constant-temperature heating magnetic stirring apparatus, instead
Temperature is answered to be 50 DEG C, then swelling 1h drips etherifying agent in 5 minutes with dropper, drips NaOH with 3 minutes again after 5min molten
Liquid, reacts 5h, obtains mixed solution.After reaction terminates, the stoste of reaction is placed in beaker and naturally cools to room temperature, add 5
The ethanol precipitation of times mixed liquor volume, is put into the refrigerating chamber of refrigerator and refrigerates 12 hours.
The beaker for being placed on refrigerating chamber is taken out after 12 hours, is filtered, the precipitation for obtaining ethanol is washed 3-5 time, is put into 60 DEG C
Vacuum drying chamber drying to constant weight.
Determine the flocculating effect of the cation-modified gamma-polyglutamic acid in seawater of synthesis
Take the cation-modified gamma-polyglutamic acids of 0.01g and be dissolved in beaker, during 100ml volumetric flasks are dissolved in surely, take 100ml and shake
Even seawater is placed in the beaker of 150ml, stirring.The cation-modified gamma-polyglutamic acid solution 1ml-3ml that addition is prepared,
Rotating speed 600r/min stirs 2min, 200r/min stirring 5min, after standing 30min, measures its turbidity.Horizontal survey 2 times, takes it
Mean value.
Embodiment 2
There is nucleophilic substitution using gamma-polyglutamic acid and 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, NaOH is catalysis
Agent, aqueous phase reactions.
Synthesizing cationic is modified gamma-polyglutamic acid
Weighing 1g gamma-polyglutamic acids adds 10ml distilled water to be placed in the round-bottomed flask of 250ml, stirs.
The 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (65% aqueous solution) for weighing 0.04mol (11.57g) are placed in beaker,
It is standby.
Weigh 0.052mol (2.08g) NaOH add 10ml it is water-soluble in beaker.It is standby.
The round-bottomed flask for being dissolved in the gamma-polyglutamic acid aqueous solution is fixed in heat collecting type constant-temperature heating magnetic stirring apparatus, instead
Temperature is answered to be 50 DEG C, then swelling 1h drips etherifying agent in 5 minutes with dropper, drips NaOH with 3 minutes again after 5min molten
Liquid, reacts 5h.
After reaction terminates, the stoste of reaction is placed in beaker and naturally cools to room temperature, add 5 times of ethanol precipitations, be put into
Refrigerate 12 hours in the refrigerating chamber of refrigerator.
The beaker for being placed on refrigerating chamber is taken out after 12 hours, is filtered, the precipitation for obtaining ethanol is washed 3-5 time, is put into 60 DEG C
Vacuum drying chamber drying to constant weight.
Determine the flocculating effect of the cation-modified gamma-polyglutamic acid in seawater of synthesis
Take the cation-modified gamma-polyglutamic acids of 0.01g and be dissolved in beaker, during 100ml volumetric flasks are dissolved in surely, take 100ml and shake
Even seawater is placed in the beaker of 150ml, stirring.The cation-modified gamma-polyglutamic acid solution 1ml-3ml that addition is prepared,
Rotating speed 600r/min stirs 2min, 200r/min stirring 5min, after standing 30min, measures its turbidity.Horizontal survey 2 times, takes it
Mean value.
Embodiment 3
There is nucleophilic substitution using gamma-polyglutamic acid and 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, NaOH is catalysis
Agent, aqueous phase reactions.
Synthesizing cationic is modified gamma-polyglutamic acid
Weighing 1g gamma-polyglutamic acids adds 10ml distilled water to be placed in the round-bottomed flask of 250ml, stirs.
The 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (65% aqueous solution) for weighing 0.07mol (20.26g) are placed in beaker,
It is standby.
Weigh 0.091mol (3.64g) NaOH add 10ml it is water-soluble in beaker.It is standby.
The round-bottomed flask for being dissolved in the gamma-polyglutamic acid aqueous solution is fixed in heat collecting type constant-temperature heating magnetic stirring apparatus, instead
Temperature is answered to be 50 DEG C, then swelling 1h drips etherifying agent in 5 minutes with dropper, drips NaOH with 3 minutes again after 5min molten
Liquid, reacts 3h.
After reaction terminates, the stoste of reaction is placed in beaker and naturally cools to room temperature, add 5 times of ethanol precipitations, be put into
Refrigerate 12 hours in the refrigerating chamber of refrigerator.
The beaker for being placed on refrigerating chamber is taken out after 12 hours, is filtered, the precipitation for obtaining ethanol is washed 3-5 time, is put into 60 DEG C
Vacuum drying chamber drying to constant weight.
Determine the flocculating effect of the cation-modified gamma-polyglutamic acid in seawater of synthesis
Take the cation-modified gamma-polyglutamic acids of 0.01g and be dissolved in beaker, during 100ml volumetric flasks are dissolved in surely, take 100ml and shake
Even seawater is placed in the beaker of 150ml, stirring.The cation-modified gamma-polyglutamic acid solution 1ml-3ml that addition is prepared,
Rotating speed 600r/min stirs 2min, 200r/min stirring 5min, after standing 30min, measures its turbidity.Horizontal survey 2 times, takes it
Mean value.
Unaccomplished matter of the present invention is known technology.
Claims (5)
1. a kind of synthetic method of cation-modified gamma-polyglutamic acid flocculating agent, it is characterized by comprising the steps of
1), gamma-polyglutamic acid is added in the reactor equipped with distilled water, stirring；Wherein, 50 ~ 100ml distilled water adds 1 ~ 10g
Gamma-polyglutamic acid；
2）, etherifying agent and alkali are dissolved into respectively in water, respectively obtain etherificate agent solution and alkali lye；
Wherein, mol ratio etherifying agent：Alkali=1：1~1.3；Described etherifying agent is 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides；It is described
Alkali be NaOH；
3）, by step 1）In the gamma-polyglutamic acid aqueous solution be heated to 30 DEG C -70 DEG C, then swelling 1h instills step 2）In
Etherificate agent solution, is added dropwise again alkali lye after 5min, react 3-7h, obtains mixed solution；
Wherein, volume ratio gamma-polyglutamic acid solution：Alkali lye：Etherificate agent solution=1：1~1.3：0.3~2；
4）, mixed liquor is naturally cooled into room temperature, add the ethanol precipitation of 3 ~ 5 times of mixed liquor volume amounts, refrigeration under 4 DEG C of degree
12 hours；
5）, the solution after refrigeration is filtered, precipitation wash with ethanol, is then dried, finally obtain it is cation-modified after γ-gather
Glutamic acid flocculant powder.
2. the synthetic method of cation-modified gamma-polyglutamic acid flocculating agent as claimed in claim 1, it is characterized by described ether
Agent solution obtains concentration and is preferably mass ratio 60 ~ 65%.
3. the synthetic method of cation-modified gamma-polyglutamic acid flocculating agent as claimed in claim 1, it is characterized by described alkali
The concentration of liquid is preferably 1.3 ~ 9.1mol/L.
4. the application process of cation-modified gamma-polyglutamic acid flocculating agent as claimed in claim 1, it is characterized by for high turbid
The seawater flocculation of degree.
5. the application process of cation-modified gamma-polyglutamic acid flocculating agent as claimed in claim 1, it is characterized by described sun
The application process of ion modification gamma-polyglutamic acid flocculating agent, specifically includes following steps：
Described cation-modified gamma-polyglutamic acid solution is added in high-turbidity seawater, then 500 ~ 700r/min stirrings 2 ~
3min, then 4 ~ 6min is stirred under 200 ~ 300r/min, stand, complete flocculation；
Wherein, the turbidity of high-turbidity seawater is 60 ~ 120NTU, and cation-modified gamma-polyglutamic acid solution is 0.005 ~ 0.03g/
100mL；Volume ratio high-turbidity seawater：Cation-modified gamma-polyglutamic acid solution=100:1~3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108083405A (en) * | 2018-02-05 | 2018-05-29 | 河北工业大学 | A kind of synthetic method and its application that gamma-polyglutamic acid flocculating agent is modified using Mannich reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3781325A (en) * | 1971-05-04 | 1973-12-25 | Upjohn Co | 15-methoxy-pgf2a |
| EP0774247A2 (en) * | 1995-11-15 | 1997-05-21 | Ajinomoto Co., Inc. | Hair care products |
| CN102492151A (en) * | 2011-12-02 | 2012-06-13 | 天津科技大学 | Preparation method of cationic paddy hull flocculating agent for sludge dredging and flocculating and dewatering |
-
2017
- 2017-01-22 CN CN201710052764.9A patent/CN106633046B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3781325A (en) * | 1971-05-04 | 1973-12-25 | Upjohn Co | 15-methoxy-pgf2a |
| EP0774247A2 (en) * | 1995-11-15 | 1997-05-21 | Ajinomoto Co., Inc. | Hair care products |
| CN102492151A (en) * | 2011-12-02 | 2012-06-13 | 天津科技大学 | Preparation method of cationic paddy hull flocculating agent for sludge dredging and flocculating and dewatering |
Non-Patent Citations (1)
| Title |
|---|
| ISHWAR B.BAJAJ·REKHA S.SINGHAL: "Flocculation Properties of Poly(γ-Glutamic Acid) Produced from Bacillus subtilis Isolate", 《ORIGINAL PAPER》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108083405A (en) * | 2018-02-05 | 2018-05-29 | 河北工业大学 | A kind of synthetic method and its application that gamma-polyglutamic acid flocculating agent is modified using Mannich reaction |
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