CN110193360A - A kind of induction crystallisation material for water treatment and preparation method thereof - Google Patents
A kind of induction crystallisation material for water treatment and preparation method thereof Download PDFInfo
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- CN110193360A CN110193360A CN201910570829.8A CN201910570829A CN110193360A CN 110193360 A CN110193360 A CN 110193360A CN 201910570829 A CN201910570829 A CN 201910570829A CN 110193360 A CN110193360 A CN 110193360A
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- water treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Abstract
The present invention provides a kind of induction crystallisation material for water treatment and preparation method thereof, it is related to water-treatment technology field, the induction crystallisation material for water treatment includes spherical core material and external coating, the spherical core material is 100-250 μm and lures brilliant material, the external coating is the magnetic modified polyethyleneimine with a thickness of 1-10 μm, it is described to lure brilliant material for quartz sand, rermilion, garnet, marble dust, concentrate powder, bentonite, diatomite, alumina silicate, ferrosilite, calcium silicates, magnesium silicate, potassium silicate, any one in sodium metasilicate, the present invention induces crystallisation material for water treatment to have splendid removal effect for the metal ion in water, it can effective decontamination cycle water, it has a very broad application prospects.
Description
Technical field
The present invention relates to water-treatment technology fields, and in particular to a kind of induction crystallisation material for water treatment and its preparation side
Method.
Background technique
Reverse osmosis (RO) technology has been widely used in all trades and professions, but in process of production, counter-infiltration system can be arranged
The concentrated water for accounting for the 25-55% of total inflow is put, according to statistics, the total release of China's industrial wastewater is 20,000,000,000/year, wherein reverse osmosis
Concentrated water drainage be 54.75 hundred million tons/year, day discharge amount be up to 15,000,000 tons, account for about the 27% of industrial wastewater total release.It is civilian
Reverse osmosis water purifier discharge of wastewater is also up to 6,000,000,000 tons/year.
High-salt wastewater is mainly derived from the waste water discharged during direct seawater utilization, including seawater is used as industry cooling
Water, industrial process waters and city domestic sewage etc..China's high-salt wastewater yield accounts for the 5% of waste water total amount, and it is annual still with
2% rate increases.Reverse osmosis concentrated water, high-salt wastewater cannot such as be dealt carefully with and direct emission, can to soil, surface water,
Marine environment etc. has an adverse effect, and the waste of a large amount of earth water resources is caused while seriously polluting natural environment.
Impurity in reverse osmosis concentrated water, high-salt wastewater containing heterogeneity and different number, the Ca in water2+、Mg2+Equal gold
Belong to the CO in ion and water3 2-、HCO3 -、SO4 2-、Cl-And NO3 -Equal anion bindings together, due to being concentrated by evaporation, are easy shape
At CaCO3、MgCO3、CaSO4、MgSO4Equal scales, and these metal ions can also adversely affect human body and environment.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of induction crystallisation material for water treatment and preparation method thereof.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of induction crystallisation material for water treatment, the material include spherical core material and external coating, and the spherical core material is
100-250 μm lures brilliant material, and the external coating is the magnetic modified polyethyleneimine with a thickness of 1-10 μm.
Further, described to lure brilliant material for quartz sand, rermilion, garnet, marble dust, concentrate powder, bentonite, silicon
Diatomaceous earth, alumina silicate, ferrosilite, calcium silicates, magnesium silicate, potassium silicate, any one in sodium metasilicate.
Further, the magnetic modified polyethyleneimine the preparation method is as follows:
Diluted hydrochloric acid dissolution is used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed in a certain ratio, and is heated up under nitrogen protection
To 60-80 DEG C, it is slowly added dropwise sodium hydroxide solution, drop Bi Houyong preservative film seal aging reacts 20-30min, then by polyethylene
Imines is added, and continues preservative film seal aging and reacts 1-1.5h, filters, after solid is washed repeatedly, vacuum drying.
Further, the mass ratio of the material of the Iron dichloride tetrahydrate and ferric chloride hexahydrate is 1:2.
Further, the substance withdrawl syndrome of sodium hydroxide solution is 1-1.5mol/L.
Above-mentioned induction crystallisation material for water treatment the preparation method is as follows:
By magnetic modified polyethyleneimine, gelatin, paraffin, brilliant material is lured to be added in dehydrated alcohol, 20-30min is stirred at room temperature
Epithio chloropropane is added again afterwards, is warming up to back flow reaction 1-2h, filter, solids washed with acetone repeatedly after 40-50 DEG C of low temperature
Drying.
Further, magnetic modified polyethyleneimine, gelatin, paraffin, lure brilliant material mass ratio be 1:0.01-0.05:
0.1-0.2:10-15.
(3) beneficial effect
The present invention provides a kind of induction crystallisation material for water treatment and preparation method thereof, have the advantages that
Induction crystallisation material for water treatment is generally quartz sand at present, but it induces crystalline rate lower, is separated by solid-liquid separation slowly, right
The shortcomings such as heavy metal ions removal effect difference, the present invention lure brilliant material surface cladding certain thickness magnetic modified in tradition
Polyethyleneimine makes that brilliant material surface is lured to have a large amount of amino groups, it on the one hand can be made with identical charge, avoid phase
Mutually flocculation deposition, on the other hand can be improved its adsorbing and removing effect to heavy metal ion, and polyethyleneimine is formed
Outer layer be conducive to the scale absorption that crystallization is formed rich in cellular structure, the present invention is net for reverse osmosis concentrated water and high-salt wastewater
Change processing, is crystallized by material induced selective, the salinity in raw water is discharged by crystallisation solidification, cleaned desalination solution can
It is directly used in front end production technology, the final regeneration for realizing water resource can also be applied to sea water desalination, experimental test card
Bright, the present invention induces crystallisation material for water treatment to have splendid removal effect for the metal ion in water, can be effectively net
Change recirculated water, has a very broad application prospects.
Specific embodiment
Embodiment 1:
A kind of induction crystallisation material for water treatment, including spherical core material and external coating, the spherical core material are 200 μm and lure crystalline substance
Material quartz sand, the external coating are the magnetic modified polyethyleneimine with a thickness of 5 μm.
Magnetic modified polyethyleneimine the preparation method is as follows:
Diluted hydrochloric acid dissolution, nitrogen protection are used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed by the mass ratio of the material 1:2
Under be warming up to 80 DEG C, be slowly added dropwise substance withdrawl syndrome be 1.2mol/L sodium hydroxide solution, drop Bi Houyong preservative film sealing
Aging reaction 20min, then polyethyleneimine is added, continue preservative film seal aging and react 1.5h, filter, solid is washed repeatedly
Afterwards, vacuum drying.
Above-mentioned induction crystallisation material for water treatment the preparation method is as follows:
Magnetic modified polyethyleneimine, gelatin, paraffin, quartz sand 1:0.02:0.1:15 in mass ratio are added to dehydrated alcohol
In, it is stirred at room temperature after 25min and epithio chloropropane is added again, be warming up to back flow reaction 1h, filter, solids washed with acetone is multiple
45 DEG C of low temperature dryings afterwards.
Embodiment 2:
A kind of induction crystallisation material for water treatment, including spherical core material and external coating, the spherical core material are 100 μm and lure crystalline substance
Material garnet, the external coating are the magnetic modified polyethyleneimine with a thickness of 10 μm.
Magnetic modified polyethyleneimine the preparation method is as follows:
Diluted hydrochloric acid dissolution, nitrogen protection are used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed by the mass ratio of the material 1:2
Under be warming up to 60-80 DEG C, be slowly added dropwise substance withdrawl syndrome be 1-1.5mol/L sodium hydroxide solution, drip Bi Houyong preservative film
Seal aging reacts 20-30min, then polyethyleneimine is added, and continues preservative film seal aging and reacts 1-1.5h, filters, Gu
After body is washed repeatedly, vacuum drying.
Above-mentioned induction crystallisation material for water treatment the preparation method is as follows:
Magnetic modified polyethyleneimine, gelatin, paraffin, garnet 1:0.01-0.05:0.1-0.2:10-15 in mass ratio are added
Enter into dehydrated alcohol, be stirred at room temperature after 20-30min and epithio chloropropane is added again, be warming up to back flow reaction 1-2h, filters,
Solids washed with acetone repeatedly after 40-50 DEG C of low temperature drying.
Embodiment 3:
A kind of induction crystallisation material for water treatment, including spherical core material and external coating, the spherical core material are 100 μm and lure crystalline substance
Material marble dust, the external coating are the magnetic modified polyethyleneimine with a thickness of 1 μm.
Magnetic modified polyethyleneimine the preparation method is as follows:
Diluted hydrochloric acid dissolution, nitrogen protection are used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed by the mass ratio of the material 1:2
Under be warming up to 60 DEG C, the sodium hydroxide solution that substance withdrawl syndrome is 1mol/L is slowly added dropwise, drop Bi Houyong preservative film sealing is old
Change reaction 20min, then polyethyleneimine is added, continues preservative film seal aging and react 1h, filter, after solid is washed repeatedly,
Vacuum drying.
Above-mentioned induction crystallisation material for water treatment the preparation method is as follows:
Magnetic modified polyethyleneimine, gelatin, paraffin, marble dust 1:0.01:0.1:10 in mass ratio are added to anhydrous
It in ethyl alcohol, is stirred at room temperature after 20min and epithio chloropropane is added again, be warming up to back flow reaction 1h, filter, solids washed with acetone
40 DEG C of low temperature dryings after repeatedly.
Embodiment 4:
A kind of induction crystallisation material for water treatment, including spherical core material and external coating, the spherical core material are 250 μm and lure crystalline substance
Material concentrate powder, the external coating are the magnetic modified polyethyleneimine with a thickness of 10 μm.
Magnetic modified polyethyleneimine the preparation method is as follows:
Diluted hydrochloric acid dissolution, nitrogen protection are used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed by the mass ratio of the material 1:2
Under be warming up to 80 DEG C, be slowly added dropwise substance withdrawl syndrome be 1.5mol/L sodium hydroxide solution, drop Bi Houyong preservative film sealing
Aging reaction 30min, then polyethyleneimine is added, continue preservative film seal aging and react 1.5h, filter, solid is washed repeatedly
Afterwards, vacuum drying.
Above-mentioned induction crystallisation material for water treatment the preparation method is as follows:
By magnetic modified polyethyleneimine, gelatin, paraffin, brilliant material 1:0.05:0.2:15 in mass ratio is lured to be added to anhydrous second
It in alcohol, is stirred at room temperature after 30min and epithio chloropropane is added again, be warming up to back flow reaction 2h, filter, solids washed with acetone is more
50 DEG C of low temperature dryings after secondary.
Embodiment 5:
A kind of induction crystallisation material for water treatment, including spherical core material and external coating, the spherical core material are 200 μm and lure crystalline substance
Material bentonite, the external coating are the magnetic modified polyethyleneimine with a thickness of 5 μm.
Magnetic modified polyethyleneimine the preparation method is as follows:
Diluted hydrochloric acid dissolution, nitrogen protection are used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed by the mass ratio of the material 1:2
Under be warming up to 60 DEG C, be slowly added dropwise substance withdrawl syndrome be 1.5mol/L sodium hydroxide solution, drop Bi Houyong preservative film sealing
Aging reaction 25min, then polyethyleneimine is added, continue preservative film seal aging and react 1h, filter, solid is washed repeatedly
Afterwards, vacuum drying.
Above-mentioned induction crystallisation material for water treatment the preparation method is as follows:
Magnetic modified polyethyleneimine, gelatin, paraffin, bentonite 1:0.02:0.1:12 in mass ratio are added to dehydrated alcohol
In, it is stirred at room temperature after 30min and epithio chloropropane is added again, be warming up to back flow reaction 1.5h, filter, solids washed with acetone is more
50 DEG C of low temperature dryings after secondary.
Embodiment 6:
A kind of induction crystallisation material for water treatment, including spherical core material and external coating, the spherical core material are 150 μm and lure crystalline substance
Material calcium silicates, the external coating are the magnetic modified polyethyleneimine with a thickness of 10 μm.
Magnetic modified polyethyleneimine the preparation method is as follows:
Diluted hydrochloric acid dissolution, nitrogen protection are used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed by the mass ratio of the material 1:2
Under be warming up to 60 DEG C, be slowly added dropwise substance withdrawl syndrome be 1.5mol/L sodium hydroxide solution, drop Bi Houyong preservative film sealing
Aging reaction 20min, then polyethyleneimine is added, continue preservative film seal aging and react 1.5h, filter, solid is washed repeatedly
Afterwards, vacuum drying.
Above-mentioned induction crystallisation material for water treatment the preparation method is as follows:
Magnetic modified polyethyleneimine, gelatin, paraffin, calcium silicates 1:0.01:0.2:10 in mass ratio are added to dehydrated alcohol
In, it is stirred at room temperature after 30min and epithio chloropropane is added again, be warming up to back flow reaction 1.5h, filter, solids washed with acetone is more
50 DEG C of low temperature dryings after secondary.
Embodiment 7:
A kind of induction crystallisation material for water treatment, including spherical core material and external coating, the spherical core material are 100 μm and lure crystalline substance
Material sodium metasilicate, the external coating are the magnetic modified polyethyleneimine with a thickness of 5 μm.
Magnetic modified polyethyleneimine the preparation method is as follows:
Diluted hydrochloric acid dissolution, nitrogen protection are used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed by the mass ratio of the material 1:2
Under be warming up to 70 DEG C, be slowly added dropwise substance withdrawl syndrome be 1.5mol/L sodium hydroxide solution, drop Bi Houyong preservative film sealing
Aging reaction 25min, then polyethyleneimine is added, continue preservative film seal aging and react 1h, filter, solid is washed repeatedly
Afterwards, vacuum drying.
Above-mentioned induction crystallisation material for water treatment the preparation method is as follows:
By magnetic modified polyethyleneimine, gelatin, paraffin, brilliant material 1:0.05:0.15:12 in mass ratio is lured to be added to anhydrous second
It in alcohol, is stirred at room temperature after 20min and epithio chloropropane is added again, be warming up to back flow reaction 2h, filter, solids washed with acetone is more
45 DEG C of low temperature dryings after secondary.
Performance test:
The following table 1 is the metal ion treatment test result that 1-3 of the embodiment of the present invention induces crystallisation material for water treatment:
Table 1:
By upper table 1 it is found that the present invention induces crystallisation material for water treatment to there is splendid removing to imitate the metal ion in water
Fruit can effectively purify raw water, have a very broad application prospects.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in process, method, article or equipment including the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (7)
1. a kind of induction crystallisation material for water treatment, which is characterized in that the material includes spherical core material and external coating, described
The brilliant material that lures that spherical core material is 100-250 μm, the external coating are the magnetic modified polyethyleneimine with a thickness of 1-10 μm.
2. as described in claim 1 induction crystallisation material for water treatment, which is characterized in that it is described lure brilliant material be quartz sand,
Rermilion, garnet, marble dust, concentrate powder, bentonite, diatomite, alumina silicate, ferrosilite, calcium silicates, magnesium silicate, silicic acid
Any one in potassium, sodium metasilicate.
3. induction crystallisation material for water treatment as described in claim 1, which is characterized in that the magnetism modified polyethyleneimine
The preparation method is as follows:
Diluted hydrochloric acid dissolution is used after Iron dichloride tetrahydrate and ferric chloride hexahydrate are mixed in a certain ratio, and is heated up under nitrogen protection
To 60-80 DEG C, it is slowly added dropwise sodium hydroxide solution, drop Bi Houyong preservative film seal aging reacts 20-30min, then by polyethylene
Imines is added, and continues preservative film seal aging and reacts 1-1.5h, filters, after solid is washed repeatedly, vacuum drying.
4. induction crystallisation material for water treatment as claimed in claim 3, which is characterized in that the Iron dichloride tetrahydrate and six
The mass ratio of the material of Ferric Chloride Hydrated is 1:2.
5. induction crystallisation material for water treatment as claimed in claim 3, which is characterized in that the amount of the substance of sodium hydroxide solution
Concentration is 1-1.5mol/L.
6. a kind of preparation method of induction crystallisation material for water treatment according to any one of claims 1 to 5, feature exist
In the specific method is as follows:
By magnetic modified polyethyleneimine, gelatin, paraffin, brilliant material is lured to be added in dehydrated alcohol, 20-30min is stirred at room temperature
Epithio chloropropane is added again afterwards, is warming up to back flow reaction 1-2h, filter, solids washed with acetone repeatedly after 40-50 DEG C of low temperature
Drying.
7. the preparation method of induction crystallisation material for water treatment as claimed in claim 6, which is characterized in that the modified poly- second of magnetism
Alkene imines, paraffin, lures the mass ratio of brilliant material for 1:0.01-0.05:0.1-0.2:10-15 at gelatin.
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| CN113368600A (en) * | 2021-05-11 | 2021-09-10 | 何建军 | Vacuum constant temperature yellow phosphorus filter |
| CN115784408A (en) * | 2022-08-31 | 2023-03-14 | 哈尔滨工业大学 | Method for removing phosphorus, fluorine and heavy metals in wastewater by using modified seed crystal for induced crystallization |
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| CN115784408A (en) * | 2022-08-31 | 2023-03-14 | 哈尔滨工业大学 | Method for removing phosphorus, fluorine and heavy metals in wastewater by using modified seed crystal for induced crystallization |
| CN115784408B (en) * | 2022-08-31 | 2023-09-12 | 哈尔滨工业大学 | Method for removing phosphorus, fluorine and heavy metals in wastewater by utilizing modified seed crystal induced crystallization |
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Application publication date: 20190903 |