CN105753128B - Polyacrylamide base heavy metal flocculant and preparation method thereof - Google Patents
Polyacrylamide base heavy metal flocculant and preparation method thereof Download PDFInfo
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- CN105753128B CN105753128B CN201610241883.4A CN201610241883A CN105753128B CN 105753128 B CN105753128 B CN 105753128B CN 201610241883 A CN201610241883 A CN 201610241883A CN 105753128 B CN105753128 B CN 105753128B
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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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- 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
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Abstract
The invention discloses a kind of polyacrylamide base heavy metal flocculants and preparation method thereof, to solve the problems, such as that existing traditional chemical precipitation method processing acid heavy metal wastewater sludge quantity is big, sediment settleability is poor, is unable to stably reaching standard.A kind of polyacrylamide base heavy metal flocculant, it is made of following raw materials according：Polyacrylamide, formaldehyde, dimethylamine, carbon disulfide, sodium hydroxide, wherein polyacrylamide solution, formaldehyde, dimethylamine volume ratio are 100:6:30~100:1.5:7.5, polyacrylamide solution, carbon disulfide, sodium hydroxide solution volume ratio are 100:10:17~100:1.5:1.5.The preparation method of above-mentioned polyacrylamide base heavy metal flocculant, including intermediate product Amino-methylated Polyacrylamide prepares and the preparation of final product.Raw material needed for the present invention is easy to get, and product preparation process is simple, and reaction condition is mild, is easy to operate and control, is easy to implement industrialized production, has a good application prospect.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of polyacrylamide base heavy metal flocculant and preparation method thereof.
Background technology
All types of industries enterprise is constantly to a large amount of heavy metal wastewater thereby of environmental emission now, since it cannot be degraded by microorganisms
And become persistent pollutant, great environmental pollution is caused, and seriously endanger human health.Therefore, people in recent years
The improvement of heavy metal wastewater thereby is attached great importance to, it is intended to remove the heavy metal in waste water with various technology and methods to reach discharge
Standard produces such as a variety of methods of chemical precipitation method, ion-exchange, electrolysis, absorption method, hyperfiltration, bioanalysis.By
In technology or economically the reason of still mostly uses chemical precipitation method processing heavy metal wastewater thereby both at home and abroad.
Chemical precipitation method processing heavy metal wastewater thereby generally includes neutralization precipitation method and sulphide precipitation, i.e., adds in waste water
Enter lime or sulphurizing salt, heavy metal ion is made to be converted into hydroxide or sulfide precipitation and be removed.Although both methods
Have the effect of certain, but as heavy metal wastewater thereby ingredient is increasingly sophisticated, discharge of wastewater requires gradually to tend to stringent, cannot expire
The requirement of sufficient discharge of wastewater, the problem of being primarily present include：1）Heavy metal wastewater thereby is generally acid waste water, need to add a large amount of lime
Sediment could be generated by so that the pH value of waste water is in alkaline condition, thus generated a large amount of sludge, increased processing cost；2）Cause
Sediment settleability is poor, and need to additionally add flocculant or flocculation aid can just be such that heavy metal is preferably removed, such as aluminium salt, iron
Salt, polyacrylamide etc., therefore increase the type and dosage of medicament；3）If other methods to be applied to the heavy metal of existing enterprise
In wastewater treatment, enterprise need to discard the structures such as existing sedimentation basin, or increase phase after the processing units such as sedimentation basin
The processing unit answered, to substantially increase processing cost and maintenance management expense.
Invention content
The object of the present invention is to provide a kind of polyacrylamide base heavy metal flocculants, are precipitated with solving existing traditional chemical
Method processing acid heavy metal wastewater sludge quantity is big, sediment settleability is poor, is unable to the problem of stably reaching standard.
It is a further object to provide a kind of preparation methods of polyacrylamide base heavy metal flocculant.
A kind of polyacrylamide base heavy metal flocculant, it is made of following raw materials according：Polyacrylamide, formaldehyde, dimethylamine,
Carbon disulfide, sodium hydroxide, wherein polyacrylamide solution, formaldehyde, dimethylamine volume ratio are 100:6:30~100:1.5:
7.5, polyacrylamide solution, carbon disulfide, sodium hydroxide solution volume ratio are 100:10:17~100:1.5:1.5.
Preferably, the polyacrylamide base heavy metal flocculant, it is made of following raw materials according：
Polyacrylamide, formaldehyde, dimethylamine, carbon disulfide, sodium hydroxide, wherein polyacrylamide solution, formaldehyde, diformazan
Amine volume ratio is 100:6:30~100:4.5:22.5, polyacrylamide solution, carbon disulfide, sodium hydroxide solution volume ratio are
100:10:17~100:5.0:8.5.
The preparation method of above-mentioned polyacrylamide base heavy metal flocculant, includes the following steps：
（1）It is prepared by intermediate product Amino-methylated Polyacrylamide：Formaldehyde and polyacrylamide solution are proportionally added into
In reactor with magnetic agitation, it is uniformly mixed, it is 57-63 DEG C to adjust reaction temperature, after being stirred to react 50-90min,
Dimethylamine is added into reactor again, the amine-methylated polyacrylamide of intermediate product is made after cooling in the reaction was continued 2.5-3.0h
Amine；
（2）The preparation of final product：It is separately added into sodium hydroxide solution and carbon disulfide into reactor, adjusts reaction temperature
Degree is 20~35 DEG C, after being stirred to react 30~60min；After reaction temperature is adjusted to 40~55 DEG C again, the reaction was continued 1.0~
2.5h is to get final product.
Preferably, the preparation method of polyacrylamide base heavy metal flocculant, step（1）It is middle by formaldehyde and polyacrylamide
Solution is proportionally added into the reactor with magnetic agitation, and it is 60 DEG C to adjust reaction temperature, after being stirred to react 50min, then to
Dimethylamine is added in reactor, intermediate product Amino-methylated Polyacrylamide is made after cooling in the reaction was continued 2.5h；
Step（2）It is middle to be separately added into sodium hydroxide solution and carbon disulfide into reactor, adjust reaction temperature be 25~
35 DEG C, after being stirred to react 30min；After reaction temperature is adjusted to 40~45 DEG C again, the reaction was continued 1.0~1.5h is to get final
Product.
Preferably, the step（1）The relative molecular mass of middle polyacrylamide is 3,000,000, is used after reactor is added
Distilled water is configured to the solution that mass percentage concentration is 1%~4%.
Preferably, the volumetric concentration of the formaldehyde is 37%~40%.
Preferably, the volumetric concentration of the dimethylamine is 30%~33%.
Preferably, for the sodium hydroxide before reactor is added, it is 40% to be first configured to mass percentage concentration with distilled water
Solution.
The present invention is intended to provide a kind of heavy metal containing wastewater treatment agent, it is heavy that it can form insoluble chelating with heavy metal ion
Starch, and the heavy metal ion in waste water can be enable to effectively remove by itself good flocculating settling characteristics；It can be not
On the basis of changing existing chemical precipitation method structures, the existing settling apparatus of enterprise is directly utilized, without increasing other processing
Unit, without additionally adding other waddings（It helps）Solidifying agent, accomplishes effluent quality qualified discharge.
Reaction mechanism of the present invention is polyacrylamide to be carried out amine-methylated modification first amine-methylated polyacrylamide is made
Then amine reacts itself and carbon disulfide, under alkaline condition by the strong coordinating group of heavy metal ion（Two thio carboxylics
Base）Be introduced into Amino-methylated Polyacrylamide macromolecular chain, prepare polyacrylamide base heavy metal flocculant, by it
Heavy metal ion in chelating-flocculation-precipitation removal waste water, sinking speed is fast, good separating effect, can be real without filtering
The processing that heavy metal wastewater thereby is now completed using existing settling apparatus, can reduce subsequent processing units number, reduce processing cost, make weight
The improvement of metallic wastewater becomes simple and practicable.
The device have the advantages that specifically including：
1, raw material needed for the present invention is easy to get, and reaction condition is mild, is easy to operate and control, and is easy to implement industrialized production,
It has a good application prospect.
2, product of the present invention can form insoluble chelating precipitation object with heavy metal ion and by itself good wadding
Solidifying settling property, enables the heavy metal ion in waste water to effectively remove, can reach the multiple actions such as chelating, flocculation, precipitation.
In heavy metal containing wastewater treatment, without additionally adding other waddings（It helps）Solidifying agent, can directly handle heavy metal in acid condition
Waste water can directly utilize the existing settling apparatus of enterprise, without being discarded or being increased other processing units.
3, product processing heavy metal wastewater thereby of the present invention is simple for process, only need to add a certain amount of product in waste water, fill
Divide stirring that can generate insoluble precipitate rapidly, sinking speed is fast, good separating effect, without filtering after sedimentation separation,
Can direct emission, without complicated equipment, easy to operation and management.It is widely used in electroplating wastewater, smelting wastewater, non-ferrous metal
The processing of the heavy metal wastewater therebies such as processing waste water, beneficiation wastewater.
Description of the drawings
Fig. 1 is process flow chart prepared by a kind of polyacrylamide base heavy metal flocculant；
Fig. 2 is a kind of structure chart of polyacrylamide base heavy metal flocculant；
Fig. 3 is a kind of FT-IR spectrograms of polyacrylamide base heavy metal flocculant.
Specific implementation mode
The following examples can further illustrate the present invention, but do not limit the invention in any way.
Raw material is that market is directly bought in embodiment.
Embodiment 1
（1）The polyacrylamide 1.0g that relative molecular mass is 3,000,000 is weighed, the reactor with magnetic agitation is added to
In, distilled water 100g is added, stirring and dissolving is made into the polyacrylamide solution that mass percentage concentration is 1.0%；Again in reactor
It is middle that commercially available formalin 1.5mL is added, reaction temperature is adjusted to 63 DEG C, is stirred to react under the conditions of low whipping speed 200r/min
After 90min；Commercially available dimethylamine solution 7.5mL is added into reactor again, is adjusted to 63 DEG C in reaction temperature, low whipping speed
Under the conditions of 200r/min, continues to be stirred to react 3h, intermediate product Amino-methylated Polyacrylamide is made after cooling；
（2）Sodium hydroxide 1.5mL and commercially available carbon disulfide 1.5mL that mass percentage concentration is 40% are added to step（1）
In reactor in, it is 25 DEG C to adjust temperature, is stirred to react 30min under the conditions of low whipping speed 200r/min, then by temperature tune
It wads a quilt with cotton to get product polypropylene amide groups heavy metal after section to the reaction was continued under the conditions of 55 DEG C, low whipping speed 200r/min 2.5h
Solidifying agent, appearance are light yellow transparent liquid.
Embodiment 2
（1）The polyacrylamide 3.0g that relative molecular mass is 3,000,000 is weighed, the reactor with magnetic agitation is added to
In, distilled water 100g is added, stirring and dissolving is made into the polyacrylamide solution that mass percentage concentration is 3.0%；Again in reactor
It is middle that commercially available formalin 4.5mL is added, reaction temperature is adjusted to 57 DEG C, under the conditions of low whipping speed 200r/min, stirring is anti-
After answering 70min；Commercially available dimethylamine solution 22.5mL is added into reactor again, 57 DEG C are adjusted in reaction temperature, in stirring speed
It spends under the conditions of 200r/min, continues to be stirred to react 2.8h, intermediate product Amino-methylated Polyacrylamide is made after cooling；
（2）Sodium hydroxide 5.5mL and commercially available carbon disulfide 5.0mL that mass percentage concentration is 40% are added to step（1）
In reactor in, it is 20 DEG C to adjust temperature, is stirred to react 60min under the conditions of low whipping speed 200r/min, then by temperature tune
It wads a quilt with cotton to get product polypropylene amide groups heavy metal after section to the reaction was continued under the conditions of 50 DEG C, low whipping speed 200r/min 1.0h
Solidifying agent, appearance are light yellow transparent liquid.
Embodiment 3
（1）The polyacrylamide 4.0g that relative molecular mass is 3,000,000 is weighed, the reactor with magnetic agitation is added to
In, distilled water 100g is added, stirring and dissolving is made into the polyacrylamide solution that mass percentage concentration is 4.0%；Again in reactor
It is middle that commercially available formalin 6.0mL is added, reaction temperature is adjusted to 60 DEG C, is stirred to react under the conditions of low whipping speed 200r/min
After 50min；Commercially available dimethylamine solution 30.0mL is added into reactor again, in 60 DEG C of reaction temperature, mixing speed 200r/min
Under the conditions of continue to be stirred to react 2.5h, intermediate product Amino-methylated Polyacrylamide is made after cooling；
（2）Sodium hydroxide 17.0mL and commercially available carbon disulfide 10.0mL that mass percentage concentration is 40% are added to step
（1）In reactor in, it is 35 DEG C to adjust temperature, is stirred to react 30min under the conditions of low whipping speed 200r/min, then by temperature
Be adjusted to 45 DEG C, after the reaction was continued under the conditions of low whipping speed 200r/min 1.0h to get product polypropylene amide groups heavy metal
Flocculant, appearance are light yellow transparent liquid.
Embodiment 4
（1）The polyacrylamide 3.0g that relative molecular mass is 3,000,000 is weighed, the reactor with magnetic agitation is added to
In, distilled water 100g is added, stirring and dissolving is made into the polyacrylamide solution that mass percentage concentration is 3.0%；Again in reactor
It is middle that commercially available formalin 4.5mL is added, reaction temperature is adjusted to 60 DEG C, is stirred to react under the conditions of low whipping speed 200r/min
After 50min；Commercially available dimethylamine solution 22.5mL is added into reactor again, in 60 DEG C of reaction temperature, mixing speed 200r/min
Under the conditions of continue to be stirred to react 2.5h, intermediate product Amino-methylated Polyacrylamide is made after cooling；
（2）Sodium hydroxide 8.5mL and commercially available carbon disulfide 5.0mL that mass percentage concentration is 40% are added to step（1）
In reactor in, it is 25 DEG C to adjust temperature, is stirred to react 30min under the conditions of low whipping speed 200r/min, then by temperature tune
It wads a quilt with cotton to get product polypropylene amide groups heavy metal after section to the reaction was continued under the conditions of 40 DEG C, low whipping speed 200r/min 1.5h
Solidifying agent, appearance are light yellow transparent liquid.
It is tested below with product made from embodiment 3 and embodiment 4, to observe its effect, embodiment 1 and embodiment
2 couples of Cd2+Removal effect it is good not as good as the effect of embodiment 3 and embodiment 4.
Application examples 1
It prepares and contains Cd2+Simulated water sample adds 3 products therefrom of embodiment and carries out experiment process to simulated water sample.Experiment condition
For：Take a concentration of 25mg/L's of 400mL to contain Cd2+Simulated water sample, it is 6.0 to adjust pH, is placed in the program-controlled coagulation test mixing of TS6-1 types
Instrument（Wuhan Hengling Technology Co., Ltd.）On, medicament is added, 2min is quickly stirred with the rotating speed of 120r/min, then with 40r/min
Rotating speed mix slowly 10min, settle 10min later, clear liquid under liquid level at 2cm taken to use 220FS type atomic absorption spectrophotometries
Photometer（VARIAN Oncology Systems）Measure remnants Cd2+Concentration, treatment effect are shown in Table 1.As shown in Table 1, the present invention is to containing Cd2+
Water sample has good removal effect, remaining Cd2+Concentration is less than national sewage comprehensive emission standard requirement（0.1mg/L）.
Application examples 2
It prepares and contains Cd2+Simulated water sample adds 4 products therefrom of embodiment and carries out experiment process to simulated water sample.Experiment condition
For：Take a concentration of 25mg/L's of 400mL to contain Cd2+Simulated water sample, it is 6.0 to adjust pH, is placed in the program-controlled coagulation test mixing of TS6-1 types
Instrument（Wuhan Hengling Technology Co., Ltd.）On, medicament is added, 2min is quickly stirred with the rotating speed of 120r/min, then with 40r/min
Rotating speed mix slowly 10min, settle 10min later, clear liquid under liquid level at 2cm taken to use 220FS type atomic absorption spectrophotometries
Photometer（VARIAN Oncology Systems）Measure remnants Cd2+Concentration, treatment effect are shown in Table 2.As shown in Table 2, the present invention is to containing Cd2+
Water sample has good removal effect, remaining Cd2+Concentration is less than national sewage comprehensive emission standard requirement（0.1mg/L）.
Application examples 3
It prepares and contains Cd2+Simulated water sample adds 4 products therefrom of embodiment and carries out experiment process to simulated water sample.Experiment condition
For：Take a concentration of 25mg/L's of 400mL to contain Cd2+Its pH value is adjusted to 4.0,5.0,6.0,7.0, is placed in by simulated water sample respectively
The program-controlled coagulation test mixing instrument of TS6-1 types（Wuhan Hengling Technology Co., Ltd.）On, medicament is added, it is fast with the rotating speed of 120r/min
Speed stirring 2min, then 10min is mixed slowly with the rotating speed of 40r/min, 10min is settled later, and the clear liquid under liquid level at 2cm is taken to adopt
With 220FS type atomic absorption spectrophotometers（VARIAN Oncology Systems）Measure remnants Cd2+Concentration, treatment effect are shown in Table 3.By table
3 it is found that the present invention to containing Cd2+Water sample has good removal effect, in acid condition remaining Cd2+Concentration can reach
National sewage comprehensive emission standard requirement（0.1mg/L）.
Application examples 4
It prepares and contains Cd2+Simulated water sample adds 4 products therefrom of embodiment and carries out experiment process to simulated water sample.Experiment condition
For：To take 400mL concentration be respectively 5,15,25,50mg/L contain Cd2+Its pH value is adjusted to 6.0, is placed in TS6-1 by simulated water sample
The program-controlled coagulation test mixing instrument of type（Wuhan Hengling Technology Co., Ltd.）On, medicament is added, is quickly stirred with the rotating speed of 120r/min
2min is mixed, then 10min is mixed slowly with the rotating speed of 40r/min, settles 10min later, the clear liquid under liquid level at 2cm is taken to use
220FS type atomic absorption spectrophotometers（VARIAN Oncology Systems）Measure remnants Cd2+Concentration, treatment effect are shown in Table 4.By table 4
It is found that the present invention contains Cd to different initial concentrations2+Water sample has good removal effect, remaining Cd2+Concentration is below state
Family's integrated wastewater discharge standard requirement（0.1mg/L）.
Fig. 3 explanations：4 products therefrom polyacrylamide base heavy metal flocculant of the embodiment of the present invention is precipitated with acetone
It is precipitated, puts the precipitate in 24 hours dry at 60 DEG C in vacuum drying chamber；Take the solid product after drying and potassium bromide mixed
It closes, grind, after tabletting, using IR Prestige-21 type infrared spectrophotometers（Japanese Shimadzu Corporation）Infrared spectrum is measured,
As a result see Fig. 3.Each peak ownership is as follows：1454cm-1The peak at place is C=S stretching vibration peaks；1122cm-1The peak at place is flexible for N-C
Vibration peak；972cm-1The peak at place is C-S stretching vibration peaks.It is successfully grafted two on polyacrylamide macromolecular chain described above
Thiocarboxylic acid base（- C (=S)-S–）, it is target product to prepare product.
Claims (7)
1. a kind of preparation method of polyacrylamide base heavy metal flocculant, it is characterised in that it includes the following steps：
（1）It is prepared by intermediate product Amino-methylated Polyacrylamide：Formaldehyde and polyacrylamide solution are proportionally added into band magnetic
In the reactor of power stirring, it is uniformly mixed, it is 57-63 DEG C to adjust reaction temperature, after being stirred to react 50-90min, then to
Dimethylamine is added in reactor, intermediate product Amino-methylated Polyacrylamide is made after cooling in the reaction was continued 2.5-3.0h；
（2）The preparation of final product：Sodium hydroxide solution and carbon disulfide are separately added into reactor, adjusting reaction temperature is
20~35 DEG C, after being stirred to react 30~60min；After reaction temperature is adjusted to 40~55 DEG C again, the reaction was continued 1.0~2.5h,
Up to final product；
Polyacrylamide solution, formaldehyde, dimethylamine volume ratio are 100:（1.5-6）:（7.5-30）, polyacrylamide solution, two
Nitric sulfid, sodium hydroxide solution volume ratio are 100:（1.5-10）:（1.5-17）.
2. the preparation method of polyacrylamide base heavy metal flocculant according to claim 1, it is characterised in that：Polypropylene
Amide solution, formaldehyde, dimethylamine volume ratio are 100:（4.5-6）:（22.5-30）, polyacrylamide solution, carbon disulfide, hydrogen
Sodium hydroxide solution volume ratio is 100:（5.0-10）:（8.5-17）.
3. the preparation method of polyacrylamide base heavy metal flocculant according to claim 1, it is characterised in that：
Step（1）It is middle that formaldehyde and polyacrylamide solution are proportionally added into the reactor with magnetic agitation, adjust reaction
Temperature is 60 DEG C, after being stirred to react 50min, then dimethylamine is added into reactor, the reaction was continued 2.5h, is made intermediate after cooling
Product Amino-methylated Polyacrylamide；
Step（2）Middle that sodium hydroxide solution and carbon disulfide are separately added into reactor, it is 25~35 DEG C to adjust reaction temperature,
After being stirred to react 30min；After reaction temperature is adjusted to 40~45 DEG C again, the reaction was continued 1.0~1.5h is to get final product.
4. the preparation method of polyacrylamide base heavy metal flocculant according to claim 1, it is characterised in that：The step
Suddenly（1）The relative molecular mass of middle polyacrylamide is 3,000,000, and it is dense with distilled water to be configured to quality percentage after reactor is added
The solution that degree is 1%~4%.
5. the preparation method of polyacrylamide base heavy metal flocculant according to claim 1, it is characterised in that：The first
The volumetric concentration of aldehyde is 37%~40%.
6. the preparation method of polyacrylamide base heavy metal flocculant according to claim 1, it is characterised in that：Described two
The volumetric concentration of methylamine is 30%~33%.
7. the preparation method of polyacrylamide base heavy metal flocculant according to claim 1, it is characterised in that：The hydrogen
Sodium oxide molybdena is first configured to the solution that mass percentage concentration is 40% before reactor is added with distilled water.
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| CN106925242B (en) * | 2017-03-20 | 2019-07-09 | 浙江工商大学 | A kind of basic fuchsin adsorbent and its preparation method and application |
| CN106927553B (en) * | 2017-03-20 | 2019-06-25 | 浙江工商大学 | A kind of starch flocculant and its preparation method and application |
| CN106946333B (en) * | 2017-04-13 | 2020-03-24 | 兰州交通大学 | Heavy metal flocculant and preparation method thereof |
| CN108211193A (en) * | 2018-01-15 | 2018-06-29 | 广东中科乐活环境科技有限公司 | A kind of fly-ash heavy metal capture high-molecular chelating agent and preparation method thereof |
| CN109626536A (en) * | 2018-12-06 | 2019-04-16 | 深圳粤鹏环保技术股份有限公司 | A kind of preparation method and applications of anion base metal agent for capturing |
| CN110041938A (en) * | 2019-05-15 | 2019-07-23 | 安徽华文塑胶科技有限公司 | A kind of heavy metal-polluted soil stabilizer and preparation method thereof |
| CN110586054B (en) * | 2019-08-23 | 2021-05-14 | 南昌三星化工实业有限公司 | Adsorbent for removing heavy metals and application thereof |
| CN110615557A (en) * | 2019-10-16 | 2019-12-27 | 镇江市和云工业废水处置有限公司 | Treatment process of electroless copper plating wastewater |
| CN110655160B (en) * | 2019-10-25 | 2022-06-10 | 江苏康净源环境科技有限公司 | Preparation method of heavy metal capture agent |
| CN111268778A (en) * | 2020-03-04 | 2020-06-12 | 广州天赐高新材料股份有限公司 | Heavy metal trapping agent and preparation method and preparation device thereof |
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| CN104277164A (en) * | 2013-07-05 | 2015-01-14 | 湖北禧邦可环保科技有限公司 | Preparation method for high polymer flocculant |
| CN104558324A (en) * | 2014-12-25 | 2015-04-29 | 上海源育节能环保科技有限公司 | Resource recycling application of heavy metals in wastewater |
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