CN105000645A - Environment-friendly water treatment agent, preparing method thereof and water treatment method - Google Patents
Environment-friendly water treatment agent, preparing method thereof and water treatment method Download PDFInfo
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- CN105000645A CN105000645A CN201510441877.9A CN201510441877A CN105000645A CN 105000645 A CN105000645 A CN 105000645A CN 201510441877 A CN201510441877 A CN 201510441877A CN 105000645 A CN105000645 A CN 105000645A
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Abstract
The invention relates to an environment-friendly water treatment agent, a preparing method thereof and a water treatment method. The environment-friendly water treatment agent comprises acrylamide oligomer/oxidized graphene/ferroferric oxide compounds, zinc modified polyacrylamide, polysilicate aluminum ferrite and sodium bicarbonate. A preparing method in which oxidized graphene is grafted on acrylamide oligomers includes the three steps of carboxylation of the oxidized graphene, preparing of carboxylation ferroferric oxide and composite reacting. By means of the water treatment agent, magnetic-field-assisting rapid flocculation and efficient recycling can be achieved; meanwhile, as the zinc modified polyacrylamide is adopted, the decomposition time of the polyacrylamide is effectively shortened, and the requirement for the environment-friendly performance is met. The water treatment method includes the steps of mixing, primary flocculation, secondary flocculation and filtering. The water treatment agent is efficiently used through a lower-layer-water backflow step, and the production cost is reduced.
Description
Technical field
The present invention relates to the technical field of water treatment, particularly relate to the water treatment method of a kind of environmentally friendly water conditioner and its preparation method and application this environmentally friendly water conditioner.
Background technology
Water conditioner is widely used in former water and sewage treatment area, can reduce the sense indexs such as the turbidity of former water, colourity.Multiple macromolecule organic, some heavy metal and radioactive substance is removed by water conditioner, both independently treatment system can be had of one's own, also can combine with other processing unit process, as pre-treatment, intermediate treatment and final treating processes, also can be used for the concentration process before sludge dewatering, improve the dewatering of mud.
But the recovery of water conditioner is comparatively stubborn problem in governance process, mainly comprise two problems, one, the yield of recovery is lower, and how improving organic efficiency is the key addressed this problem; Its two, degradation process is complicated, and no matter be the water conditioner or residual water conditioner that reclaim, ensure that it is effectively degraded, be the key factor preventing secondary pollution from producing.Therefore, needing that exploitation is a kind of badly can high efficiente callback and the environmentally friendly water conditioner of very fast degraded.
Summary of the invention
The water conditioner organic efficiency that the present invention is intended to for composite water disposal agent in prior art is not high, the technical problems such as degradation rate is not ideal enough, a kind of environmentally friendly water conditioner and preparation method thereof is provided, and the water treatment method of this environmentally friendly water conditioner of a kind of application is provided, by the compound of magnetic substance in the present invention, the rapid subsidence of throw out can be realized under the action of a magnetic field, greatly improve the organic efficiency of water conditioner, zinc modification polyacrylamide is adopted to improve the degraded of water conditioner, both synergies improve the environment friendly of water conditioner.In addition, the present invention also adopts lower layer of water technique of backflow to realize the efficient multiplexing of water conditioner, reduces production cost, improves water treatment efficiency.
First, the invention provides a kind of environmentally friendly water conditioner, comprise the following component with weight parts:
Acrylamide oligomers/graphene oxide/ferroferric oxide compound 2 ~ 10,
Zinc modification polyacrylamide 28 ~ 65,
Poly aluminium iron silicate 20 ~ 40,
Sodium bicarbonate 1 ~ 5.
In the environmentally friendly water conditioner that the present invention discloses, introduce and be compounded with the graphene oxide of Z 250, the matrix material of acrylamide oligomers, utilize the magnetic of Z 250, the throw out formed after achieving water conditioner flocculation can sharp separation under magnetic field condition.In addition, contriver have employed acrylamide oligomers in this mixture and is grafted on the design on graphene oxide, graphene oxide receives in recent years and pays close attention to widely, wherein most important reason is its high-ratio surface sum extensively adsorption property of excellence, in the present invention, have employed acrylamide oligomers and modification is carried out to it, improve flocculation ability on the one hand, take graphene oxide as base material, the acrylamide oligomers of grafting is stretched out from surface of graphene oxide, form many dentalations, be conducive to the formation of colloid, improve the effect of flocculation; On the other hand, heavy metal ion, poisonous small molecules, especially benzene-like compounds pollutent has extremely strong Adsorption effect, for the water body realizing complicated Pollution System source has efficient detergent power.Therefore, the invention of this mixture reaches the double effects improving flocculating effect and flocculation rate, and this never exists in prior art.The more important thing is, the introducing of magnetic substance greatly improves the organic efficiency of water conditioner, and adopt zinc modification polyacrylamide to improve the degraded of water conditioner, both synergies improve the environment friendly of water conditioner.
Concrete, acrylamide oligomers/graphene oxide/ferroferric oxide compound comprises graphene oxide 2.5 ~ 9wt%, Z 250 0.5 ~ 1% and acrylamide oligomers 90 ~ 97wt%, and described acrylamide oligomers molecular weight is 5000 ~ 20000.
For improving overall flocculating effect, be convenient to the formation of larger micelle, and improve the degradation effect of water conditioner, the zinc modification Molecular Weight for Polyacrylamide simultaneously added is 200 ~ 1,000 ten thousand, and ion degree is 50% ~ 80%.
For realizing segmentation flocculation, the water technology of adapt to repeatedly dosing, repeatedly flocculating, adopt zinc modification polyacrylamide comprise: molecular weight is the zinc modification polyacrylamide 10 ~ 30wt% of 200 ~ 4,000,000, molecular weight be 400 ~ 8,000,000 zinc modification polyacrylamide 40% ~ 50wt% and molecular weight be 800 ~ 1,000 ten thousand zinc modification polyacrylamide 20% ~ 40wt%.
Secondly, present invention also offers a kind of preparation method of environmentally friendly water conditioner, it is characterized in that, comprise the following steps:
(1) graphene oxide is carboxylated
In the graphene oxide water solution of 1 ~ 10mg/mL, add sodium hydroxide and Mono Chloro Acetic Acid, hybrid reaction 1 ~ 10 hour, be separated, wash, obtain carboxylated graphene oxide;
(2) preparation of carboxylated Z 250
Trivalent iron salt, sodium acrylate, anhydrous sodium acetate and ethylene glycol mixture are transferred in reactor, react at 200 DEG C, after cooling, through ethanol, deionized water wash, obtain the Z 250 of surface carboxyl groups;
(3) preparation of acrylamide oligomers/graphene oxide/ferroferric oxide compound
In DMSO, mix carboxylated graphene oxide, the Z 250 of surface carboxyl groups and acrylamide oligomers, add EDCI, back flow reaction at 45 DEG C, be separated, washing, obtain acrylamide oligomers/graphene oxide/ferroferric oxide compound;
(4) preparation of zinc modification polyacrylamide
Zinc nitrate is dripped, wherein acrylamide and Zn in acrylamide solution
2+mol ratio is 100:1 ~ 5, is warming up to 30 ~ 65 DEG C; Add the mixture of ammonium sulfate, sodium bisulfite, urea and EDTA, wherein, ammonium sulfate: sodium bisulfite: urea: EDTA=70:15:10:9; Namely reaction obtains the zinc modification polyacrylamide of different molecular weight for 2 ~ 10 hours;
(5) preparation of environmentally friendly water conditioner
More than 45 DEG C, acrylamide oligomers/graphene oxide/ferroferric oxide compound, zinc modification polyacrylamide are mixed in proportion also Temperature fall and, to room temperature, add poly aluminium iron silicate, sodium bicarbonate successively, mix.
As follows with weight parts of each component:
Acrylamide oligomers/graphene oxide/ferroferric oxide compound 2 ~ 10,
Zinc modification polyacrylamide 28 ~ 65,
Poly aluminium iron silicate 20 ~ 40,
Sodium bicarbonate 1 ~ 5.
According to grafting needs, control carboxylated degree by adjustment carboxylation process, preferably, graphene oxide water solution in step (1): sodium hydroxide: Mono Chloro Acetic Acid=1L:1 ~ 2g:1 ~ 2g.
Same, the control of grafting amount also can by controlling the raw material dosage in grafting process, preferably, DMSO in step (3): carboxylated graphene oxide: the Z 250 of surface carboxyl groups: acrylamide oligomers: EDCI=1L:2.5 ~ 9g:0.5 ~ 1g:90 ~ 97g:10 ~ 100g.
Finally, the invention provides and a kind ofly apply the method that above-mentioned water conditioner carries out water treatment, it is characterized in that, at least comprise the steps:
A. mix stages: former water is introduced mixing pit, adds above-mentioned environmentally friendly water conditioner, mix;
B. in the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation, magnetic field separation throw out is adopted;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds above-mentioned environmentally friendly water conditioner, again flocculate in the second flocculation basin in flow process, adopts magnetic field separation throw out;
D. filtration stage: the water after again flocculating in step C is filtered by filter plant.
Further, for improving the utilising efficiency of water conditioner, step C ' refluxing stage is also comprised: the lower layer of water after initial flocculation in step B is passed back into mixing pit.
According to the particular case of former water, in steps A, environmentally friendly water conditioner adds the amount of former water is 10 ~ 500mg/L; In step C, environmentally friendly water conditioner adds the amount of water is 1 ~ 100mg/L.
Compared to prior art, beneficial effect of the present invention is:
(1) water conditioner secondary pollution is little, the existence of graphene oxide, effectively improves the cohesive force of micelle, the secondary pollution that the diffusion decreasing relevant monomer in the agent of flocculation process sewerage disposing causes; The introducing of magnetic substance greatly improves the organic efficiency of water conditioner, and adopt zinc modification polyacrylamide to improve the degraded of water conditioner, both synergies improve the environment friendly of water conditioner.
(2) flocculation rate is fast, and flocculating settling efficiency is high, and turbidity removal, decoloring ability are strong.Employing composite water disposal agent is filled a prescription, and combining the feature performance benefit of organic polymer water conditioner, coagulant aids, inorganic polymer water conditioner, through repeatedly verifying, coordinating the electrocharge effect of each water conditioner, accomplished the optimization of flocculating effect.Introduce Z 250, make formed flocculation micelle possess magnetic, adopt the booster action in magnetic field to accelerate the formation of micelle.Simultaneously under the effect of the polyacrylamide of gradient molecular weight, be conducive to being formed fast by little and large of micelle.The quick raising of both cooperative achievement flocculation rates, under kindred circumstances, treatment time of water shortens more than 60%.
(3) cost effectively reduces, and by being drawn respectively by levels water in flocculation process, improve the effective rate of utilization of water conditioner, the extraction of upper water, decreasing the pressure of subsequent processes; The backflow of lower layer of water, adequately achieves the multiplexing of water conditioner, and through measuring and calculating, with regard to drinking water treatment standard, every cube of cost of water treatment reduces about 5%; With regard to industrial sewage preliminary treatment for regard to middle water quality standard, every cube of cost of water treatment reduces about 7%.
Embodiment
(1) preparation of environmentally friendly water conditioner
Embodiment 1-1
(1) graphene oxide is carboxylated
In the graphene oxide water solution of 5mg/mL, add sodium hydroxide and Mono Chloro Acetic Acid, graphene oxide water solution: sodium hydroxide: Mono Chloro Acetic Acid=1L:2g:2g, hybrid reaction 1 hour, be separated, wash, obtain carboxylated graphene oxide;
(2) preparation of carboxylated Z 250
Iron trichloride, sodium acrylate, anhydrous sodium acetate and ethylene glycol mixture are transferred in reactor, wherein during the mixing of iron trichloride, sodium acrylate, anhydrous sodium acetate and ethylene glycol, feed ratio is 27g:75g:75g:1000ml, react at 200 DEG C, after cooling, through ethanol, deionized water wash, obtain the Z 250 of surface carboxyl groups;
(3) preparation of acrylamide oligomers/graphene oxide/ferroferric oxide compound
Carboxylated graphene oxide, the Z 250 of surface carboxyl groups and acrylamide oligomers is mixed in DMSO, add EDCI, wherein, DMSO: carboxylated graphene oxide: the Z 250 of surface carboxyl groups: acrylamide oligomers: EDCI=1L:7.5g:0.5g:90g:50g.Back flow reaction at 45 DEG C, is separated, washs, obtain acrylamide oligomers/graphene oxide/ferroferric oxide compound;
(4) preparation of zinc modification polyacrylamide
Zinc nitrate is dripped, wherein acrylamide and Zn in acrylamide solution
2+mol ratio is 100:5, is warming up to 60 DEG C; Add the mixture of ammonium sulfate, sodium bisulfite, urea and EDTA, wherein, ammonium sulfate: sodium bisulfite: urea: EDTA=70:15:10:9; Namely reaction obtains the zinc modification polyacrylamide of different molecular weight for 2 ~ 10 hours;
(5) preparation of environmentally friendly water conditioner
More than 45 DEG C, acrylamide oligomers/graphene oxide/ferroferric oxide compound, zinc modification polyacrylamide are mixed in proportion also Temperature fall and, to room temperature, add poly aluminium iron silicate, sodium bicarbonate successively, mix.
As follows with weight parts of each component:
Acrylamide oligomers/graphene oxide/ferroferric oxide compound 10,
Zinc modification polyacrylamide 65,
Poly aluminium iron silicate 40,
Sodium bicarbonate 5.
Embodiment 1-2
In the present embodiment, the preparation process of environmentally friendly water conditioner, as embodiment 1-1, only adjusts to some extent in the proportioning of each component.The parts by weight of each component are as follows:
Acrylamide oligomers/graphene oxide/ferroferric oxide compound 8,
Zinc modification polyacrylamide 55,
Poly aluminium iron silicate 35,
Sodium bicarbonate 5.
Embodiment 1-3
In the present embodiment, the preparation process of environmentally friendly water conditioner, as embodiment 1-1, only adjusts to some extent in the proportioning of each component.The parts by weight of each component are as follows:
Acrylamide oligomers/graphene oxide/ferroferric oxide compound 6,
Zinc modification polyacrylamide 60,
Poly aluminium iron silicate 30,
Sodium bicarbonate 5.
Embodiment 1-4
In the present embodiment, the preparation process of environmentally friendly water conditioner, as embodiment 1-1, only adjusts to some extent in the proportioning of each component.The parts by weight of each component are as follows:
Acrylamide oligomers/graphene oxide/ferroferric oxide compound 4
Zinc modification polyacrylamide 45
Poly aluminium iron silicate 40
Sodium bicarbonate 5.
Embodiment 1-5
In the present embodiment, the preparation process of environmentally friendly water conditioner, as embodiment 1-1, only adjusts to some extent in the proportioning of each component.The parts by weight of each component are as follows:
Acrylamide oligomers/graphene oxide/ferroferric oxide compound 2,
Zinc modification polyacrylamide 30,
Poly aluminium iron silicate 40,
Sodium bicarbonate 2.
Comparative example 1-6
Have employed first component of not adding Z 250 in this comparative example to contrast.
The parts by weight of each component are as follows:
Acrylamide oligomers grafted graphene oxide 10,
Polyacrylamide 65,
Poly aluminium iron silicate 40,
Sodium bicarbonate 5.
(2) the former water of environmentally friendly water conditioner process
1. former water parameter: pH:7.51, turbidity (NTU): 75.6; COD(mg/L): 58.05; Colourity: 240 times; Temperature: room temperature.
2. experiment condition: get 5 beakers and contain into former water 1L respectively, 200rpm rapid stirring 30s, 30s terminates to add the water conditioner 200mg configured in embodiment 1-1 to 1-5 respectively in rear 5 beakers, changes rotating speed 40rpm, stirs 15min, after low rate mixing terminates, stop stirring, liquid leaves standstill, and places magnet in beaker bottom, after flocculation terminates, under getting liquid level, 2cm place water quality detects.
3. experimental result: corresponding to the water sample of the water conditioner process configured in embodiment 1-1 to 1-5, be labeled as result 2-1 to 2-5, corresponding to comparative example 1-6, be labeled as result 2-6, design parameter list is see table 1.
Table 1
Known by above-mentioned experimental data, the removal efficiency adopting environmentally friendly water conditioner of the present invention can realize turbidity, COD and colourity entirety improves, and wherein, turbidity removal rate is up to 94.31%, the clearance of COD is up to 96.72%, and chroma removal rate is up to 95.42%.The introducing of magnetic substance not only increases flocculation efficiency, greatly reduces flocculation time especially and is less than original 11.1%.
(3) impact of original sub-block technique
In following experiment, the flocculation basin capacity of employing is 100 cubes of standard analog ponds, controls overall water intake velocity 20 cubic meters/hour, and entirety goes out water speed 20 cubic meters/hour.
Embodiment 3-1
A. mix stages: former water is introduced mixing pit, adds the environmentally friendly water conditioner in embodiment 1-1, mix;
B. in the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation, magnetic field separation throw out is adopted to adopt magnetic field separation throw out;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds environmentally friendly water conditioner described above, again flocculate in the second flocculation basin in flow process, adopts magnetic field separation throw out;
C ' refluxing stage: the lower layer of water after initial flocculation in step B is passed back into mixing pit;
D. filtration stage: the water after again flocculating in step C is filtered by filter plant.
In steps A, environmentally friendly water conditioner adds the amount of former water is 200mg/L; In step C, environmentally friendly water conditioner adds the amount of water is 100mg/L.
Embodiment 3-2
A. mix stages: former water is introduced mixing pit, adds the environmentally friendly water conditioner in embodiment 1-1, mix;
B. in the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation, magnetic field separation throw out is adopted;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds environmentally friendly water conditioner described above, again flocculate in the second flocculation basin in flow process, adopts magnetic field separation throw out;
D. filtration stage: the water after again flocculating in step C is filtered by filter plant.
In steps A, environmentally friendly water conditioner adds the amount of former water is 200mg/L; In step C, environmentally friendly water conditioner adds the amount of water is 100mg/L.
Embodiment 3-3
A. mix stages: former water is introduced mixing pit, adds the environmentally friendly water conditioner in embodiment 1-1, mix;
B. in the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation, magnetic field separation throw out is adopted;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds environmentally friendly water conditioner described above, again flocculate in the second flocculation basin in flow process, adopts magnetic field separation throw out;
C ' refluxing stage: the lower layer of water after initial flocculation in step B is passed back into mixing pit;
D. filtration stage: the water after again flocculating in step C is filtered by filter plant.
In steps A, environmentally friendly water conditioner adds the amount of former water is 150mg/L; In step C, environmentally friendly water conditioner adds the amount of water is 150mg/L.
Embodiment 3-4
A. mix stages: former water is introduced mixing pit, adds the environmentally friendly water conditioner in embodiment 1-1, mix;
B. in the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation, magnetic field separation throw out is adopted;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds environmentally friendly water conditioner described above, again flocculate in the second flocculation basin in flow process, adopts magnetic field separation throw out;
C ' refluxing stage: the lower layer of water after initial flocculation in step B is passed back into mixing pit.
D. filtration stage: the water after again flocculating in step C is filtered by filter plant.
In steps A, environmentally friendly water conditioner adds the amount of former water is 250mg/L; In step C, environmentally friendly water conditioner adds the amount of water is 50mg/L.
Comparative example 3-5
A. mix stages: former water is introduced mixing pit, adds the environmentally friendly water conditioner in embodiment 1-1, mix;
B. flocculated stage: the water after mixing in steps A is introduced the first flocculation basin and flocculates, adopts magnetic field separation throw out;
C. filtration stage: the water flocculated in step B is filtered by filter plant.
In steps A, environmentally friendly water conditioner adds the amount of former water is 300mg/L.
Experimental result: corresponding to the water technology of embodiment 3-1 to 3-4, comparative example 3-5, before and after process, the design parameter list of water is see table 2.
Table 2
Known by above-mentioned experimental data, (1) compared to a flocculating settling technique, adopt secondary flocculating settling technique effectively can improve water treatment capacity, water conditioner addition in suitable adjustment initial flocculation and again flocculation process can realize the adjustment to water treatment efficiency, under former regimen condition complicated situation, be conducive to technique adjustment and realize usefulness raising; (2) under same process step, the lower layer of water technique of backflow clearance to the turbidity of former water, COD, colourity is adopted all to be significantly improved.
Claims (4)
1. an environmentally friendly water conditioner, is characterized in that, comprises the following component with weight parts:
Acrylamide oligomers/graphene oxide/ferroferric oxide compound 2 ~ 10,
Zinc modification polyacrylamide 28 ~ 65,
Poly aluminium iron silicate 20 ~ 40,
Sodium bicarbonate 1 ~ 5.
2. environmentally friendly water conditioner according to claim 1, it is characterized in that, described acrylamide oligomers/graphene oxide/ferroferric oxide compound comprises graphene oxide 2.5 ~ 9wt%, Z 250 0.5 ~ 1% and acrylamide oligomers 90 ~ 97wt%, and described acrylamide oligomers molecular weight is 5000 ~ 20000.
3. a preparation method for the environmentally friendly water conditioner according to claim 1-2, is characterized in that, comprise the following steps:
(1) graphene oxide is carboxylated
In the graphene oxide water solution of 1 ~ 10mg/mL, add sodium hydroxide and Mono Chloro Acetic Acid, hybrid reaction 1 ~ 10 hour, be separated, wash, obtain carboxylated graphene oxide;
(2) preparation of carboxylated Z 250
Trivalent iron salt, sodium acrylate, anhydrous sodium acetate and ethylene glycol mixture are transferred in reactor, react at 200 DEG C, after cooling, through ethanol, deionized water wash, obtain the Z 250 of surface carboxyl groups;
(3) preparation of acrylamide oligomers/graphene oxide/ferroferric oxide compound
In DMSO, mix carboxylated graphene oxide, the Z 250 of surface carboxyl groups and acrylamide oligomers, add EDCI, back flow reaction at 45 DEG C, be separated, washing, obtain acrylamide oligomers/graphene oxide/ferroferric oxide compound;
(4) preparation of zinc modification polyacrylamide
Zinc nitrate is dripped, wherein acrylamide and Zn in acrylamide solution
2+mol ratio is 100:1 ~ 5, is warming up to 30 ~ 65 DEG C; Add the mixture of ammonium sulfate, sodium bisulfite, urea and EDTA, wherein, ammonium sulfate: sodium bisulfite: urea: EDTA=70:15:10:9; Namely reaction obtains the zinc modification polyacrylamide of different molecular weight for 2 ~ 10 hours;
(5) preparation of environmentally friendly water conditioner
More than 45 DEG C, acrylamide oligomers/graphene oxide/ferroferric oxide compound, zinc modification polyacrylamide are mixed in proportion also Temperature fall and, to room temperature, add poly aluminium iron silicate, sodium bicarbonate successively, mix.
4. a method for water treatment, is characterized in that, at least comprises the steps:
A. mix stages: former water is introduced mixing pit, adds the environmentally friendly water conditioner as described in claim 1-3, mix;
B. in the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation, magnetic field separation throw out is adopted;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, the environmentally friendly water conditioner as described in claim 1-3 is added in flow process, again flocculate in the second flocculation basin, adopt magnetic field separation throw out;
D. filtration stage: the water after again flocculating in step C is filtered by filter plant.
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| CN105314724A (en) * | 2015-11-25 | 2016-02-10 | 苏州书瑞环保科技有限公司 | Composite water treatment material and preparing method thereof |
| CN107224961A (en) * | 2017-07-31 | 2017-10-03 | 陕西科技大学 | Carboxylated graphene oxide/ferriferrous oxide nano compound adsorbent for handling waste water containing chrome tanning and preparation method thereof |
| CN109455776A (en) * | 2018-11-14 | 2019-03-12 | 陈云 | A kind of sewage scavenging material and preparation method thereof |
| CN110563960A (en) * | 2019-09-16 | 2019-12-13 | 中国科学院生态环境研究中心 | Nitrogen-doped iron-based graphene gel, and preparation method and application thereof |
| CN114751491A (en) * | 2022-04-29 | 2022-07-15 | 郑州大学 | Synchronous and efficient purification method and system for micro-plastic and heavy metal pollutants in water environment |
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| JPH06114209A (en) * | 1992-10-07 | 1994-04-26 | Tokiwa Kensetsu Kk | Water treatment agent and water method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105314724A (en) * | 2015-11-25 | 2016-02-10 | 苏州书瑞环保科技有限公司 | Composite water treatment material and preparing method thereof |
| CN107224961A (en) * | 2017-07-31 | 2017-10-03 | 陕西科技大学 | Carboxylated graphene oxide/ferriferrous oxide nano compound adsorbent for handling waste water containing chrome tanning and preparation method thereof |
| CN109455776A (en) * | 2018-11-14 | 2019-03-12 | 陈云 | A kind of sewage scavenging material and preparation method thereof |
| CN110563960A (en) * | 2019-09-16 | 2019-12-13 | 中国科学院生态环境研究中心 | Nitrogen-doped iron-based graphene gel, and preparation method and application thereof |
| CN114751491A (en) * | 2022-04-29 | 2022-07-15 | 郑州大学 | Synchronous and efficient purification method and system for micro-plastic and heavy metal pollutants in water environment |
| CN114751491B (en) * | 2022-04-29 | 2023-08-04 | 郑州大学 | Synchronous and efficient purification method and system for micro-plastics and heavy metal pollutants in water environment |
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