CN109205748A - A kind of flocculant and preparation method for heavy metal-polluted water process - Google Patents
A kind of flocculant and preparation method for heavy metal-polluted water process Download PDFInfo
- Publication number
- CN109205748A CN109205748A CN201811273232.9A CN201811273232A CN109205748A CN 109205748 A CN109205748 A CN 109205748A CN 201811273232 A CN201811273232 A CN 201811273232A CN 109205748 A CN109205748 A CN 109205748A
- Authority
- CN
- China
- Prior art keywords
- parts
- weight
- heavy metal
- flocculant
- reaction
- 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.)
- Withdrawn
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
- C02F1/52—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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention relates to heavy metal-polluted water treatment fields, provide a kind of flocculant and preparation method for heavy metal-polluted water process.It is modified that this method first carries out hydroxylating to chitosan, then aqueous solution is made with starch, and cross-linking reaction is carried out on the surface of fine silicon dioxide aeroge, then by Polyacrylamide Grafted in cross-linked chitosan/starch surface, methylolation further is carried out to polyacrylamide using formalin to be modified, and the flocculant for heavy metal-polluted water process is made.It is compared with the traditional method, heavy metal flocculant prepared by the present invention, with very big specific surface area and porosity, density is low to bubble through the water column, and favorable dispersibility, polyacrylamide is increased to the adsorption site of heavy metal ion especially by modification, and flocculating effect significantly improves, and the loss by dissolution for passing through the cross-linking modified free functional group for preventing chitosan, keeps flocculating effect more stable.
Description
Technical field
The invention belongs to the technical fields of heavy metal-polluted water process, provide a kind of flocculation for heavy metal-polluted water process
Agent and preparation method.
Background technique
Heavy metal containing sewage is mainly from machining, non-ferrous metal metallurgy, plating, leather processing and part chemical company
Deng.Heavy metal contaminants usually have acute or chronic toxicity, can not be disappeared by self purification, but can pass through Food chain
Enrichment, to endanger human health.Heavy metal pollution of water body has become one of the environmental problem of global most serious.Currently, a huge sum of money
There are many processing method for belonging to sewage: bio-flocculation process, absorption method, chemical precipitation method, electrochemical process, flocculence etc..Wherein, it flocculates
Method at home and abroad occupies an important position in heavy metal containing sewage treatment research.
In the flocculence of heavy metal-polluted water process, the research of flocculant is the core of flocculation technique, and type and property are straight
Connect influence treatment effect.Flocculant can be divided into low molecule and high polymer coagulant by molecular mass height；By functional group's property and
The electrically charged situation of institute, is divided into nonionic, anion, cation and amphoteric flocculating agent etc. after dissociation；It can be divided into from composition inorganic
High polymer coagulant, organic polymer coargulator, microbial flocculant and composite flocculation agent.
The wastewater treatment efficiency of the flocculant of single component is often not ideal enough, and therefore, composite flocculation agent becomes development
Inexorable trend.The shortcomings that different flocculants advantage and disadvantage after compound are complementary, overcome single flocculant narrow scope of application, thus
Flocculating effect is improved, use scope is expanded.Composite flocculation agent mainly has Composite Inorganic Polymer Flocculants, You Jifu at present
Close flocculant and inorganic-organic composite flocculating agent.It is wherein more to the report of inorganic-organic composite flocculating agent, it is composite flocculation
The research of agent and priority application.
Chinese invention patent application number 201710241445.2 discloses a kind of heavy metal flocculant and preparation method thereof.
The heavy metal flocculant of the invention is prepared by the following method to obtain: (1) by formaldehyde and dimethylamine hybrid reaction 0.5 at room temperature
After ~ 1.0h, 30 ~ 50 DEG C are adjusted the temperature to, PAM 1 ~ 3h of solution reaction that molecular weight is 100,000 ~ 3,000,000 is added, obtains APAM；
Wherein, PAM, formaldehyde, dimethylamine the mass ratio of the material be 1:(1 ~ 1.5): (1 ~ 2)；(2) by TGA and mass concentration be 0.5 ~
2.0% APAM mixing, adjusting pH value in reaction is 3.0 ~ 7.0, and 1 ~ 4h is reacted at a temperature of 15 ~ 45 DEG C, obtains heavy metal flocculant
MAAPAM；Wherein, the mass ratio of the material of APAM and TGA is 1:(1 ~ 4).But the flocculation of heavy metal flocculant made from the invention is imitated
Rate is lower.
Chinese invention patent application number 201611048672.5 discloses a kind of heavy metal-polluted water process flocculant, packet
It includes and is made of the raw material of following parts by weight: 40 ~ 60 parts of granite, 10 ~ 20 parts of basalt, 10 ~ 20 parts of peridotite, clay mineral
15 ~ 25 parts, 11 ~ 23 parts of active carbon, 8 ~ 16 parts of chitosan, 14 ~ 26 parts of epoxy resin, 10 ~ 18 parts of sepiolite, montmorillonite 7 ~ 13
Part, 9 ~ 15 parts of alginic acid, 6 ~ 14 parts of gelatin, 15 ~ 25 parts of alum, 5 ~ 10 parts of barium sulphide, 11 ~ 16 parts of cellulose base, nano-silica
Change admire 4 ~ 8 parts, 6 ~ 14 parts of hydrotalcite, 13 ~ 19 parts of silica gel and 9 ~ 19 parts of NaHS, with 5 ~ 10 parts of inorganic acid and water, it is made into 80 ~
The solution of 120ppm；It is easy to operate in flocculant in the invention, secondary pollution will not be generated, can adsorb and precipitate in sewage
Heavy metal, reduce water pollution, improve purifying water effect.But the flocculating effect of the flocculant of the invention still needs further to be mentioned
It rises.
In conclusion the flocculating effect of the common heavy metal flocculant of the prior art is poor, the heavy metal ion in sewage
Removal effect is undesirable, therefore develops a kind of flocculant that can efficiently remove the heavy metal ion in sewage, there is important meaning
Justice.
Summary of the invention
As it can be seen that the flocculating effect of the common heavy metal flocculant of the prior art is poor, the removal of heavy metal ions in sewage
Effect is undesirable.In response to this, the present invention proposes a kind of flocculant and preparation method for heavy metal-polluted water process, institute
Flocculant has very big specific surface area and porosity, density is low to bubble through the water column, and favorable dispersibility, especially by changing
Property increase polyacrylamide to the adsorption site of heavy metal ion, flocculating effect significantly improves, and by cross-linking modified anti-
The only loss by dissolution of the free functional group of chitosan, keeps flocculating effect more stable.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of preparation method of the flocculant for heavy metal-polluted water process, the specific steps of the heavy metal flocculant preparation are such as
Under:
(1) chitosan being added in the sodium hydroxide solution of mass concentration 20 ~ 30%, then stirring swelling carries out cryogenic freezing,
It is centrifuged off extra sodium hydroxide solution after defrosting, and n-butanol is added and stirs 20 ~ 30min, mass concentration 3 is further added
~ 5% Ammonia and propylene oxide, heating reflux reaction, cooled and filtered, n-butanol are washed and are dried, and hydroxypropyl is made
Base enclosure glycan；
(2) hydroxypropyl chitosan made from step (1) is added in deionized water with plant amylum and is dissolved, is then added micro-
Fine silica aeroge, is stirred to being uniformly dispersed, and then adjusts pH value to 8 ~ 9, glutaraldehyde is added and is reacted, reaction terminates
PH value is adjusted afterwards to neutrality, and washs, dry, and is made using aerosil as core, using cross-linked chitosan/starch as shell
Composite particles；
(3) it disperses composite particles made from step (2) in deionized water, is continually fed into nitrogen, acrylamide is then added
And ammonium persulfate, temperature reaction, it is filtered, washs, dries after reaction, obtained Polyacrylamide Grafted is modified compound
Particle；
(4) it disperses modified composite particles made from step (3) in deionized water, the formaldehyde that mass concentration 20 ~ 30% is added is molten
Liquid adjusts pH value to 8 ~ 9, and temperature reaction is filtered after reaction, washs, dries, and obtained hydroxymethyl polyacrylamide connects
The modified composite particles of branch, that is, be used for the flocculant of heavy metal-polluted water process.
Preferably, the parts by weight of step (1) each raw material are, 15 ~ 20 parts by weight of chitosan, sodium hydroxide solution 20 ~
25 parts by weight, 41 ~ 57 parts by weight of n-butanol, 4 ~ 6 parts by weight of Ammonia, 4 ~ 8 parts by weight of propylene oxide.
Preferably, the temperature of step (1) described heating reflux reaction is 70 ~ 80 DEG C, and the time is 4 ~ 5h.
Preferably, the parts by weight of step (2) each raw material are 4 ~ 8 parts by weight of hydroxypropyl chitosan, 8 ~ 15 weight of starch
Part, 48 ~ 66 parts by weight of deionized water, 20 ~ 25 parts by weight of fine silicon dioxide aeroge, 2 ~ 4 parts by weight of glutaraldehyde.
Preferably, the temperature of step (2) described cross-linking reaction is 35 ~ 40 DEG C, and the time is 2 ~ 3h.
Preferably, the parts by weight of step (3) each raw material are 20 ~ 30 parts by weight of composite particles, deionized water 58 ~ 74
Parts by weight, 5 ~ 10 parts by weight of acrylamide, 1 ~ 2 parts by weight of ammonium persulfate.
Preferably, the temperature of step (3) described reaction is 40 ~ 45 DEG C, and the time is 4 ~ 5h.
Preferably, the parts by weight of step (4) each raw material are modified 12 ~ 18 parts by weight of composite particles, deionized water 52
~ 68 parts by weight, 20 ~ 30 parts by weight of formalin.
Preferably, the temperature of step (4) described reaction is 60 ~ 70 DEG C, and the time is 1 ~ 1.5h.
The present invention also provides a kind of flocculations for heavy metal-polluted water process that a kind of above-mentioned preparation method is prepared
Agent.The heavy metal flocculant is modified by first carrying out hydroxylating to chitosan, aqueous solution is then made with starch, and micro-
The surface of fine silica aeroge carries out cross-linking reaction, then by Polyacrylamide Grafted in cross-linked chitosan/starch surface,
Methylolation modification is further carried out to polyacrylamide using formalin and is made.
Inner core support of the present invention using fine silicon dioxide aeroge as flocculant.Firstly, fine silicon dioxide
Aeroge has very big specific surface area and porosity, using fine silicon dioxide aeroge as structure basis, can make oxidant layer of flocculating
Specific surface area also greatly increase, to increase effective contact area of flocculant and sewage；Second, fine silicon dioxide airsetting
Glue has the characteristics that density is small, can reduce the global density of flocculant, flocculant is made to bubble through the water column, convenient for separating with water body.
The present invention is first modified chitosan, increases the water-soluble of chitosan, in the water-soluble of chitosan and starch
In liquid, chitosan molecule chain is easier to mutually wind with starch molecular chain and intert.It is further cross-linked with each other, makes chitosan/shallow lake
Combination of the powder on fine silicon dioxide aeroge surface is more secured, while the amino of chitosan can be prevented molten due to protonation
Solution is lost, and keeps absorption property more stable.
Since polyacrylamide has good flocculating effect to heavy metal ion, and it is anti-monomer polymerization can to occur with starch
It answers, by Polyacrylamide Grafted in cross-linked chitosan/starch surface, the polyacrylamide after grafting contains not in pairs the present invention
Electronics, be very easy to attract each other to form stable chelate with metal cation.Further, it is carried out using formalin
Modified, obtained hydroxymethyl polyacrylamide has more active sites to the absorption of heavy metal ion, makes flocculating effect more
For ideal.
It is and existing in conclusion the present invention provides a kind of flocculant and preparation method for heavy metal-polluted water process
Technology is compared, and the feature and excellent effect protruded is:
1. heavy metal flocculant prepared by the present invention has very big specific surface area and porosity, effective contact surface with sewage
Product is big.
2. heavy metal flocculant prepared by the present invention, density is low to bubble through the water column, convenient for separating with water body, and dispersibility is good
It is good.
3. heavy metal flocculant prepared by the present invention passes through the dissolution stream of the cross-linking modified free functional group for preventing chitosan
It loses, keeps flocculating effect more stable.
4. heavy metal flocculant prepared by the present invention increases absorption of the polyacrylamide to heavy metal ion by modification
Site, flocculating effect significantly improve.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) chitosan is added in the sodium hydroxide solution of mass concentration 24%, then stirring swelling carries out cryogenic freezing, thaws
It is centrifuged off extra sodium hydroxide solution afterwards, and n-butanol stirring 26min is added, the hydrogen-oxygen of mass concentration 4% is further added
Change ammonium salt solution and propylene oxide, heating reflux reaction, cooled and filtered, n-butanol are washed and dried, hydroxypropyl chitosan is made；
The temperature of heating reflux reaction is 76 DEG C, time 4.5h；The parts by weight of each raw material are 17 parts by weight of chitosan, sodium hydroxide
22 parts by weight of solution, 51 parts by weight of n-butanol, 5 parts by weight of Ammonia, 5 parts by weight of propylene oxide；
(2) hydroxypropyl chitosan made from step (1) is added in deionized water with plant amylum and is dissolved, is then added micro-
Fine silica aeroge, is stirred to being uniformly dispersed, and then adjusts pH value to 8.5, glutaraldehyde is added and is reacted, reaction terminates
PH value is adjusted afterwards to neutrality, and washs, dry, and is made using aerosil as core, using cross-linked chitosan/starch as shell
Composite particles；The temperature of cross-linking reaction is 37 DEG C, time 2.5h；The parts by weight of each raw material are 5 weight of hydroxypropyl chitosan
Part, 11 parts by weight of starch, 58 parts by weight of deionized water, 23 parts by weight of fine silicon dioxide aeroge, 3 parts by weight of glutaraldehyde；
(3) it disperses composite particles made from step (2) in deionized water, is continually fed into nitrogen, acrylamide is then added
And ammonium persulfate, temperature reaction, it is filtered, washs, dries after reaction, obtained Polyacrylamide Grafted is modified compound
Particle；The temperature of reaction is 43 DEG C, time 4.5h；The parts by weight of each raw material are 24 parts by weight of composite particles, deionized water 68
Parts by weight, 7 parts by weight of acrylamide, 1 parts by weight of ammonium persulfate；
(4) it disperses modified composite particles made from step (3) in deionized water, the formalin of mass concentration 26% is added,
PH value is adjusted to 8.5, temperature reaction is filtered after reaction, washs, dries, and hydroxymethyl polyacrylamide grafting is made
Modified composite particles are used for the flocculant of heavy metal-polluted water process；The temperature of reaction is 66 DEG C, time 1h；Each raw material
Parts by weight be modified 15 parts by weight of composite particles, 61 parts by weight of deionized water, 24 parts by weight of formalin.
Embodiment 2
(1) chitosan is added in the sodium hydroxide solution of mass concentration 22%, then stirring swelling carries out cryogenic freezing, thaws
It is centrifuged off extra sodium hydroxide solution afterwards, and n-butanol stirring 23min is added, the hydrogen of mass concentration 3.5% is further added
Ammonium hydroxide solution and propylene oxide, heating reflux reaction, cooled and filtered, n-butanol are washed and are dried, and hydroxypropyl is made
Sugar；The temperature of heating reflux reaction is 72 DEG C, time 5h；The parts by weight of each raw material are 16 parts by weight of chitosan, sodium hydroxide
22 parts by weight of solution, 52 parts by weight of n-butanol, 5 parts by weight of Ammonia, 5 parts by weight of propylene oxide；
(2) hydroxypropyl chitosan made from step (1) is added in deionized water with plant amylum and is dissolved, is then added micro-
Fine silica aeroge, is stirred to being uniformly dispersed, and then adjusts pH value to 8, glutaraldehyde is added and is reacted, after reaction
PH value is adjusted to neutrality, and washs, dry, is made using aerosil as core, answering using cross-linked chitosan/starch as shell
Close particle；The temperature of cross-linking reaction is 36 DEG C, time 3h；The parts by weight of each raw material are that 5 parts by weight of hydroxypropyl chitosan are formed sediment
10 parts by weight of powder, 61 parts by weight of deionized water, 21 parts by weight of fine silicon dioxide aeroge, 3 parts by weight of glutaraldehyde；
(3) it disperses composite particles made from step (2) in deionized water, is continually fed into nitrogen, acrylamide is then added
And ammonium persulfate, temperature reaction, it is filtered, washs, dries after reaction, obtained Polyacrylamide Grafted is modified compound
Particle；The temperature of reaction is 41 DEG C, time 5h；The parts by weight of each raw material are 22 parts by weight of composite particles, 71 weight of deionized water
Measure part, 6 parts by weight of acrylamide, 1 parts by weight of ammonium persulfate；
(4) it disperses modified composite particles made from step (3) in deionized water, the formalin of mass concentration 23% is added,
PH value is adjusted to 8, temperature reaction is filtered after reaction, washs, dries, and hydroxymethyl polyacrylamide grafting is made and changes
Property composite particles, that is, be used for heavy metal-polluted water process flocculant；The temperature of reaction is 62 DEG C, time 1.5h；Each raw material
Parts by weight be modified 14 parts by weight of composite particles, 64 parts by weight of deionized water, 24 parts by weight of formalin.
Embodiment 3
(1) chitosan is added in the sodium hydroxide solution of mass concentration 28%, then stirring swelling carries out cryogenic freezing, thaws
It is centrifuged off extra sodium hydroxide solution afterwards, and n-butanol stirring 27min is added, the hydrogen of mass concentration 4.5% is further added
Ammonium hydroxide solution and propylene oxide, heating reflux reaction, cooled and filtered, n-butanol are washed and are dried, and hydroxypropyl is made
Sugar；The temperature of heating reflux reaction is 78 DEG C, time 4h；The parts by weight of each raw material are 19 parts by weight of chitosan, sodium hydroxide
24 parts by weight of solution, 44 parts by weight of n-butanol, 6 parts by weight of Ammonia, 7 parts by weight of propylene oxide；
(2) hydroxypropyl chitosan made from step (1) is added in deionized water with plant amylum and is dissolved, is then added micro-
Fine silica aeroge, is stirred to being uniformly dispersed, and then adjusts pH value to 9, glutaraldehyde is added and is reacted, after reaction
PH value is adjusted to neutrality, and washs, dry, is made using aerosil as core, answering using cross-linked chitosan/starch as shell
Close particle；The temperature of cross-linking reaction is 39 DEG C, time 2h；The parts by weight of each raw material are that 7 parts by weight of hydroxypropyl chitosan are formed sediment
12 parts by weight of powder, 53 parts by weight of deionized water, 24 parts by weight of fine silicon dioxide aeroge, 4 parts by weight of glutaraldehyde；
(3) it disperses composite particles made from step (2) in deionized water, is continually fed into nitrogen, acrylamide is then added
And ammonium persulfate, temperature reaction, it is filtered, washs, dries after reaction, obtained Polyacrylamide Grafted is modified compound
Particle；The temperature of reaction is 44 DEG C, time 4h；The parts by weight of each raw material are 27 parts by weight of composite particles, 63 weight of deionized water
Measure part, 8 parts by weight of acrylamide, 2 parts by weight of ammonium persulfate；
(4) it disperses modified composite particles made from step (3) in deionized water, the formalin of mass concentration 28% is added,
PH value is adjusted to 9, temperature reaction is filtered after reaction, washs, dries, and hydroxymethyl polyacrylamide grafting is made and changes
Property composite particles, that is, be used for heavy metal-polluted water process flocculant；The temperature of reaction is 67 DEG C, time 1h；Each raw material
Parts by weight are modified 16 parts by weight of composite particles, 57 parts by weight of deionized water, 27 parts by weight of formalin.
Embodiment 4
(1) chitosan is added in the sodium hydroxide solution of mass concentration 20%, then stirring swelling carries out cryogenic freezing, thaws
It is centrifuged off extra sodium hydroxide solution afterwards, and n-butanol stirring 20min is added, the hydrogen-oxygen of mass concentration 3% is further added
Change ammonium salt solution and propylene oxide, heating reflux reaction, cooled and filtered, n-butanol are washed and dried, hydroxypropyl chitosan is made；
The temperature of heating reflux reaction is 70 DEG C, time 5h；The parts by weight of each raw material are that 15 parts by weight of chitosan, sodium hydroxide are molten
20 parts by weight of liquid, 57 parts by weight of n-butanol, 4 parts by weight of Ammonia, 4 parts by weight of propylene oxide；
(2) hydroxypropyl chitosan made from step (1) is added in deionized water with plant amylum and is dissolved, is then added micro-
Fine silica aeroge, is stirred to being uniformly dispersed, and then adjusts pH value to 8, glutaraldehyde is added and is reacted, after reaction
PH value is adjusted to neutrality, and washs, dry, is made using aerosil as core, answering using cross-linked chitosan/starch as shell
Close particle；The temperature of cross-linking reaction is 35 DEG C, time 3h；The parts by weight of each raw material are that 4 parts by weight of hydroxypropyl chitosan are formed sediment
8 parts by weight of powder, 66 parts by weight of deionized water, 20 parts by weight of fine silicon dioxide aeroge, 2 parts by weight of glutaraldehyde；
(3) it disperses composite particles made from step (2) in deionized water, is continually fed into nitrogen, acrylamide is then added
And ammonium persulfate, temperature reaction, it is filtered, washs, dries after reaction, obtained Polyacrylamide Grafted is modified compound
Particle；The temperature of reaction is 40 DEG C, time 5h；The parts by weight of each raw material are 20 parts by weight of composite particles, 74 weight of deionized water
Measure part, 5 parts by weight of acrylamide, 1 parts by weight of ammonium persulfate；
(4) it disperses modified composite particles made from step (3) in deionized water, the formalin of mass concentration 20% is added,
PH value is adjusted to 8, temperature reaction is filtered after reaction, washs, dries, and hydroxymethyl polyacrylamide grafting is made and changes
Property composite particles, that is, be used for heavy metal-polluted water process flocculant；The temperature of reaction is 60 DEG C, time 1.5h；Each raw material
Parts by weight be modified 12 parts by weight of composite particles, 68 parts by weight of deionized water, 20 parts by weight of formalin.
Embodiment 5
(1) chitosan is added in the sodium hydroxide solution of mass concentration 30%, then stirring swelling carries out cryogenic freezing, thaws
It is centrifuged off extra sodium hydroxide solution afterwards, and n-butanol stirring 30min is added, the hydrogen-oxygen of mass concentration 5% is further added
Change ammonium salt solution and propylene oxide, heating reflux reaction, cooled and filtered, n-butanol are washed and dried, hydroxypropyl chitosan is made；
The temperature of heating reflux reaction is 80 DEG C, time 4h；The parts by weight of each raw material are that 20 parts by weight of chitosan, sodium hydroxide are molten
25 parts by weight of liquid, 41 parts by weight of n-butanol, 6 parts by weight of Ammonia, 8 parts by weight of propylene oxide；
(2) hydroxypropyl chitosan made from step (1) is added in deionized water with plant amylum and is dissolved, is then added micro-
Fine silica aeroge, is stirred to being uniformly dispersed, and then adjusts pH value to 9, glutaraldehyde is added and is reacted, after reaction
PH value is adjusted to neutrality, and washs, dry, is made using aerosil as core, answering using cross-linked chitosan/starch as shell
Close particle；The temperature of cross-linking reaction is 40 DEG C, time 2h；The parts by weight of each raw material are that 8 parts by weight of hydroxypropyl chitosan are formed sediment
15 parts by weight of powder, 48 parts by weight of deionized water, 25 parts by weight of fine silicon dioxide aeroge, 4 parts by weight of glutaraldehyde；
(3) it disperses composite particles made from step (2) in deionized water, is continually fed into nitrogen, acrylamide is then added
And ammonium persulfate, temperature reaction, it is filtered, washs, dries after reaction, obtained Polyacrylamide Grafted is modified compound
Particle；The temperature of reaction is 45 DEG C, time 4h；The parts by weight of each raw material are 30 parts by weight of composite particles, 58 weight of deionized water
Measure part, 10 parts by weight of acrylamide, 2 parts by weight of ammonium persulfate；
(4) it disperses modified composite particles made from step (3) in deionized water, the formalin of mass concentration 30% is added,
PH value is adjusted to 9, temperature reaction is filtered after reaction, washs, dries, and hydroxymethyl polyacrylamide grafting is made and changes
Property composite particles, that is, be used for heavy metal-polluted water process flocculant；The temperature of reaction is 70 DEG C, time 1h；Each raw material
Parts by weight are modified 18 parts by weight of composite particles, 52 parts by weight of deionized water, 30 parts by weight of formalin.
Embodiment 6
(1) chitosan is added in the sodium hydroxide solution of mass concentration 25%, then stirring swelling carries out cryogenic freezing, thaws
It is centrifuged off extra sodium hydroxide solution afterwards, and n-butanol stirring 25min is added, the hydrogen-oxygen of mass concentration 4% is further added
Change ammonium salt solution and propylene oxide, heating reflux reaction, cooled and filtered, n-butanol are washed and dried, hydroxypropyl chitosan is made；
The temperature of heating reflux reaction is 75 DEG C, time 4.5h；The parts by weight of each raw material are 18 parts by weight of chitosan, sodium hydroxide
22 parts by weight of solution, 49 parts by weight of n-butanol, 5 parts by weight of Ammonia, 6 parts by weight of propylene oxide；
(2) hydroxypropyl chitosan made from step (1) is added in deionized water with plant amylum and is dissolved, is then added micro-
Fine silica aeroge, is stirred to being uniformly dispersed, and then adjusts pH value to 8.5, glutaraldehyde is added and is reacted, reaction terminates
PH value is adjusted afterwards to neutrality, and washs, dry, and is made using aerosil as core, using cross-linked chitosan/starch as shell
Composite particles；The temperature of cross-linking reaction is 38 DEG C, time 2.5h；The parts by weight of each raw material are 6 weight of hydroxypropyl chitosan
Part, 12 parts by weight of starch, 57 parts by weight of deionized water, 22 parts by weight of fine silicon dioxide aeroge, 9 parts by weight of glutaraldehyde；
(3) it disperses composite particles made from step (2) in deionized water, is continually fed into nitrogen, acrylamide is then added
And ammonium persulfate, temperature reaction, it is filtered, washs, dries after reaction, obtained Polyacrylamide Grafted is modified compound
Particle；The temperature of reaction is 42 DEG C, time 4.5h；The parts by weight of each raw material are 25 parts by weight of composite particles, deionized water 66
Parts by weight, 8 parts by weight of acrylamide, 1 parts by weight of ammonium persulfate；
(4) it disperses modified composite particles made from step (3) in deionized water, the formalin of mass concentration 25% is added,
PH value is adjusted to 8.5, temperature reaction is filtered after reaction, washs, dries, and hydroxymethyl polyacrylamide grafting is made
Modified composite particles are used for the flocculant of heavy metal-polluted water process；The temperature of reaction is 65 DEG C, time 1.5h；Each original
The parts by weight of material are modified 15 parts by weight of composite particles, 60 parts by weight of deionized water, 25 parts by weight of formalin.
Comparative example 1
In preparation process, chitosan and starch are not crosslinked, other preparation conditions and embodiment 6 are consistent.
Comparative example 2
In preparation process, formalin is not used, polyacrylamide is modified, other preparation conditions and embodiment 6 are consistent.
Performance test:
Removal of heavy metal ions rate: it prepares respectively contain Cd first2+、Pb2+、Cu2+、Hg2+Heavy metal wastewater thereby sample, concentration is
100mg/L is added flocculant produced by the present invention according to the amount of 5mg/L, is placed on six blenders, first with 200 ~ 220r/min
Revolving speed stir 2min, the revolving speed of 100r/min stirs 5min, then stirs 8min with the revolving speed of 50 ~ 60r/min, stand 15min,
The clear liquid under liquid level at 2cm is taken, measures the concentration of each heavy metal ion respectively using fluorimetry, according to the changing value of concentration
With the ratio of initial concentration, removal of heavy metal ions rate can be calculated.
The data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of preparation method of the flocculant for heavy metal-polluted water process, which is characterized in that the heavy metal flocculant system
It is standby that specific step is as follows:
(1) chitosan being added in the sodium hydroxide solution of mass concentration 20 ~ 30%, then stirring swelling carries out cryogenic freezing,
It is centrifuged off extra sodium hydroxide solution after defrosting, and n-butanol is added and stirs 20 ~ 30min, mass concentration 3 is further added
~ 5% Ammonia and propylene oxide, heating reflux reaction, cooled and filtered, n-butanol are washed and are dried, and hydroxypropyl is made
Base enclosure glycan；
(2) hydroxypropyl chitosan made from step (1) is added in deionized water with plant amylum and is dissolved, is then added micro-
Fine silica aeroge, is stirred to being uniformly dispersed, and then adjusts pH value to 8 ~ 9, glutaraldehyde is added and is reacted, reaction terminates
PH value is adjusted afterwards to neutrality, and washs, dry, and is made using aerosil as core, using cross-linked chitosan/starch as shell
Composite particles；
(3) it disperses composite particles made from step (2) in deionized water, is continually fed into nitrogen, acrylamide is then added
And ammonium persulfate, temperature reaction, it is filtered, washs, dries after reaction, obtained Polyacrylamide Grafted is modified compound
Particle；
(4) it disperses modified composite particles made from step (3) in deionized water, the formaldehyde that mass concentration 20 ~ 30% is added is molten
Liquid adjusts pH value to 8 ~ 9, and temperature reaction is filtered after reaction, washs, dries, and obtained hydroxymethyl polyacrylamide connects
The modified composite particles of branch, that is, be used for the flocculant of heavy metal-polluted water process.
2. a kind of preparation method of the flocculant for heavy metal-polluted water process according to claim 1, it is characterised in that: step
Suddenly the parts by weight of (1) described each raw material are, 15 ~ 20 parts by weight of chitosan, 20 ~ 25 parts by weight of sodium hydroxide solution, n-butanol 41 ~
57 parts by weight, 4 ~ 6 parts by weight of Ammonia, 4 ~ 8 parts by weight of propylene oxide.
3. a kind of preparation method of the flocculant for heavy metal-polluted water process according to claim 1, it is characterised in that: step
Suddenly the temperature of (1) described heating reflux reaction is 70 ~ 80 DEG C, and the time is 4 ~ 5h.
4. a kind of preparation method of the flocculant for heavy metal-polluted water process according to claim 1, it is characterised in that: step
Suddenly the parts by weight of (2) described each raw material are 4 ~ 8 parts by weight of hydroxypropyl chitosan, 8 ~ 15 parts by weight of starch, deionized water 48 ~ 66
Parts by weight, 20 ~ 25 parts by weight of fine silicon dioxide aeroge, 2 ~ 4 parts by weight of glutaraldehyde.
5. a kind of preparation method of the flocculant for heavy metal-polluted water process according to claim 1, it is characterised in that: step
Suddenly the temperature of (2) described cross-linking reaction is 35 ~ 40 DEG C, and the time is 2 ~ 3h.
6. a kind of preparation method of the flocculant for heavy metal-polluted water process according to claim 1, it is characterised in that: step
Suddenly the parts by weight of (3) described each raw material are, 20 ~ 30 parts by weight of composite particles, 58 ~ 74 parts by weight of deionized water, acrylamide 5 ~
10 parts by weight, 1 ~ 2 parts by weight of ammonium persulfate.
7. a kind of preparation method of the flocculant for heavy metal-polluted water process according to claim 1, it is characterised in that: step
Suddenly the temperature of (3) described reaction is 40 ~ 45 DEG C, and the time is 4 ~ 5h.
8. a kind of preparation method of the flocculant for heavy metal-polluted water process according to claim 1, it is characterised in that: step
Suddenly the parts by weight of (4) described each raw material are that modified 12 ~ 18 parts by weight of composite particles, 52 ~ 68 parts by weight of deionized water, formaldehyde are molten
20 ~ 30 parts by weight of liquid.
9. a kind of preparation method of the flocculant for heavy metal-polluted water process according to claim 1, it is characterised in that: step
Suddenly the temperature of (4) described reaction is 60 ~ 70 DEG C, and the time is 1 ~ 1.5h.
10. a kind of flocculant for heavy metal-polluted water process that any one of claim 1 ~ 9 preparation method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811273232.9A CN109205748A (en) | 2018-10-30 | 2018-10-30 | A kind of flocculant and preparation method for heavy metal-polluted water process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811273232.9A CN109205748A (en) | 2018-10-30 | 2018-10-30 | A kind of flocculant and preparation method for heavy metal-polluted water process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109205748A true CN109205748A (en) | 2019-01-15 |
Family
ID=64997272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811273232.9A Withdrawn CN109205748A (en) | 2018-10-30 | 2018-10-30 | A kind of flocculant and preparation method for heavy metal-polluted water process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109205748A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252877A (en) * | 2020-03-09 | 2020-06-09 | 董群雄 | Oilfield sewage treatment flocculant and preparation method thereof |
| CN113004005A (en) * | 2021-03-08 | 2021-06-22 | 浙江忠信新型建材股份有限公司 | Cement-based grouting material prepared based on machine-made sand |
| CN113501572A (en) * | 2021-07-28 | 2021-10-15 | 扬州科苑化工有限公司 | Special flocculant for municipal refuse leachate and preparation method thereof |
| CN114195235A (en) * | 2020-09-02 | 2022-03-18 | 上海昶法新材料有限公司 | Flocculating agent, raw material composition thereof, and preparation method and application thereof |
| CN115073669A (en) * | 2022-06-30 | 2022-09-20 | 东华大学 | Preparation method of cellulose-based adsorption flocculation material for wastewater treatment |
| CN116002834A (en) * | 2023-01-16 | 2023-04-25 | 山东蓝昕环保测试分析有限公司 | Heavy metal organic coupling agent and treatment method applied to sewage treatment |
| CN117583031A (en) * | 2024-01-18 | 2024-02-23 | 上格环境科技（上海）有限公司 | Heavy metal sewage treatment agent and preparation process thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3103499A (en) * | 1959-04-02 | 1963-09-10 | Thermal stabilization of oxymethylene | |
| EP1663879A1 (en) * | 2003-09-11 | 2006-06-07 | Rhodia UK Limited | Treatment of iron sulphide deposits |
| CN101224413A (en) * | 2007-09-29 | 2008-07-23 | 大连理工大学 | Water-soluble cationic polymer adsorption material and applications thereof |
| CN101463144A (en) * | 2009-01-12 | 2009-06-24 | 武汉理工大学 | Hydroxypropyl chitosan / oxidized sodium alginate self-crosslinking antibacterial hydrogel material |
| CN104804139A (en) * | 2015-05-21 | 2015-07-29 | 南京大学 | Flocculation sterilization difunctional grafting starch water treatment agent and preparation method thereof |
| CN105854789A (en) * | 2016-05-06 | 2016-08-17 | 王泽陆 | Industrial wastewater treatment material and preparation method thereof |
| CN108017127A (en) * | 2017-11-14 | 2018-05-11 | 青岛卓森纳生物工程有限公司 | A kind of nano-high molecule carboxymethyl chitosan sewage treatment drug and processing method |
| CN108176379A (en) * | 2017-12-22 | 2018-06-19 | 苏州纳贝通环境科技有限公司 | A kind of preparation method of Industrial waste water treatment agent |
| CN108299598A (en) * | 2018-03-09 | 2018-07-20 | 陕西科技大学 | A kind of preparation method of cationic high molecular polymer |
| CN108359103A (en) * | 2018-02-05 | 2018-08-03 | 南京师范大学 | A kind of hydrophobically modified chitosan flocculant and its preparation method and application |
-
2018
- 2018-10-30 CN CN201811273232.9A patent/CN109205748A/en not_active Withdrawn
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3103499A (en) * | 1959-04-02 | 1963-09-10 | Thermal stabilization of oxymethylene | |
| EP1663879A1 (en) * | 2003-09-11 | 2006-06-07 | Rhodia UK Limited | Treatment of iron sulphide deposits |
| CN101224413A (en) * | 2007-09-29 | 2008-07-23 | 大连理工大学 | Water-soluble cationic polymer adsorption material and applications thereof |
| CN101463144A (en) * | 2009-01-12 | 2009-06-24 | 武汉理工大学 | Hydroxypropyl chitosan / oxidized sodium alginate self-crosslinking antibacterial hydrogel material |
| CN104804139A (en) * | 2015-05-21 | 2015-07-29 | 南京大学 | Flocculation sterilization difunctional grafting starch water treatment agent and preparation method thereof |
| CN105854789A (en) * | 2016-05-06 | 2016-08-17 | 王泽陆 | Industrial wastewater treatment material and preparation method thereof |
| CN108017127A (en) * | 2017-11-14 | 2018-05-11 | 青岛卓森纳生物工程有限公司 | A kind of nano-high molecule carboxymethyl chitosan sewage treatment drug and processing method |
| CN108176379A (en) * | 2017-12-22 | 2018-06-19 | 苏州纳贝通环境科技有限公司 | A kind of preparation method of Industrial waste water treatment agent |
| CN108359103A (en) * | 2018-02-05 | 2018-08-03 | 南京师范大学 | A kind of hydrophobically modified chitosan flocculant and its preparation method and application |
| CN108299598A (en) * | 2018-03-09 | 2018-07-20 | 陕西科技大学 | A kind of preparation method of cationic high molecular polymer |
Non-Patent Citations (2)
| Title |
|---|
| 杨芳: "羧甲基纤维素与丙烯酰胺接枝共聚及共聚物的性能", 《高分子材料科学与工程》 * |
| 马凤国: "羧甲基纤维素接枝共聚物的制备及对铜离子的吸附性能", 《高分子材料科学与工程》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252877A (en) * | 2020-03-09 | 2020-06-09 | 董群雄 | Oilfield sewage treatment flocculant and preparation method thereof |
| CN114195235A (en) * | 2020-09-02 | 2022-03-18 | 上海昶法新材料有限公司 | Flocculating agent, raw material composition thereof, and preparation method and application thereof |
| CN114195235B (en) * | 2020-09-02 | 2024-03-15 | 上海昶法新材料有限公司 | Flocculant, raw material composition thereof, and preparation method and application thereof |
| CN113004005A (en) * | 2021-03-08 | 2021-06-22 | 浙江忠信新型建材股份有限公司 | Cement-based grouting material prepared based on machine-made sand |
| CN113501572A (en) * | 2021-07-28 | 2021-10-15 | 扬州科苑化工有限公司 | Special flocculant for municipal refuse leachate and preparation method thereof |
| CN115073669A (en) * | 2022-06-30 | 2022-09-20 | 东华大学 | Preparation method of cellulose-based adsorption flocculation material for wastewater treatment |
| CN115073669B (en) * | 2022-06-30 | 2023-10-20 | 东华大学 | Preparation method of cellulose-based adsorption flocculation material for wastewater treatment |
| CN116002834A (en) * | 2023-01-16 | 2023-04-25 | 山东蓝昕环保测试分析有限公司 | Heavy metal organic coupling agent and treatment method applied to sewage treatment |
| CN117583031A (en) * | 2024-01-18 | 2024-02-23 | 上格环境科技（上海）有限公司 | Heavy metal sewage treatment agent and preparation process thereof |
| CN117583031B (en) * | 2024-01-18 | 2024-03-19 | 上格环境科技（上海）有限公司 | Heavy metal sewage treatment agent and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109205748A (en) | A kind of flocculant and preparation method for heavy metal-polluted water process | |
| CN111068626B (en) | Magnetic dithiocarbamic acid modified chitosan microsphere as well as preparation method and application thereof | |
| CN111068632A (en) | Lead ion composite adsorbent and preparation method thereof | |
| CN107930600B (en) | Preparation method of nano composite water purification material | |
| CN104001479B (en) | A kind of inorganic mineral water treatment agent and preparation method thereof | |
| Chen et al. | Influence of operating parameters on the performance of magnetic seeding flocculation | |
| CN110372078A (en) | A kind of high efficiency composition flocculant and preparation method thereof | |
| CN113385144A (en) | Porous material adsorbent and preparation method and application thereof | |
| CN108295812B (en) | Graphene oxide composite membrane for selectively removing metal ions in water, and preparation method and application thereof | |
| CN114735795B (en) | Sodium alginate-diatomite composite magnetic flocculant and preparation method thereof | |
| CN112473630A (en) | Composite graphene chitosan aerogel and preparation method and application thereof | |
| CN106630082B (en) | Preparation method of polyvinyl chloride-based flocculant | |
| CN111450805A (en) | Chitosan-based lead ion imprinted adsorbent and preparation method thereof | |
| CN109663581B (en) | Method for preparing cobalt (II) ion imprinting composite membrane by using N-pyrrolidinylacrylamide | |
| CN111203197A (en) | Adsorbing material based on epoxy and amino crosslinking and preparation method thereof | |
| KR101739286B1 (en) | Manufacturing method of adsorbent for phosphorus chemisorption | |
| CN115650448B (en) | Composite flocculant based on modified diatomite and application thereof | |
| CN110357393B (en) | Nano flocculant for sludge sedimentation and preparation method thereof | |
| CN112591868B (en) | PH adjusting compound agent and application thereof in precipitation adsorption treatment of fluorine-containing water body | |
| CN110040831B (en) | Preparation method of sodium alginate-polymethacryloxyethyl trimethyl ammonium chloride organic flocculant | |
| CN103007588A (en) | Method for purifying ammonium sulfate mother liquor produced from sintering flue gas through ammonia method desulfurization process | |
| CN114146681A (en) | Composite material for treating nitrogen-containing sewage and preparation method and application thereof | |
| CN113788912A (en) | Preparation method and application of imprinting material for removing nitrate in drinking underground water | |
| CN111039344A (en) | Nano diatom composite water purifying agent and preparation method thereof | |
| CN108057425B (en) | Sewage treatment adsorbent and preparation method 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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190115 |