CN109569499A - A kind of preparation method and application of mercapto-functionalized flyash - Google Patents
A kind of preparation method and application of mercapto-functionalized flyash Download PDFInfo
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- CN109569499A CN109569499A CN201811336776.5A CN201811336776A CN109569499A CN 109569499 A CN109569499 A CN 109569499A CN 201811336776 A CN201811336776 A CN 201811336776A CN 109569499 A CN109569499 A CN 109569499A
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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 preparation method and applications of mercapto-functionalized flyash, using hydroxylating flyash after processing as carrier, surface grafting sulfydryl, stable sulfydryl complex can be formed with heavy metal ion, through the above way, mercapto-functionalized flyash produced by the present invention can carry out good absorption to heavy metal ion in water, for administering waters Heavy Metal Pollution Control.Low, the at low cost, simple process of the method for the present invention energy consumption, raw material are easy to get, and preparation process and product have good environment compatibility.The flyash prepared has high-specific surface area, has good adsorptivity and stability to heavy metal ion in aqueous solution, and application conditions are mild, and suitable metal is extensive, is expected to become a kind of novel water treatment absorbent.
Description
Technical field
The invention belongs to environmental monitorings and contamination control field, in particular to a kind of for administering heavy metal pollution in waters
Mercapto-functionalized flyash preparation method and application.
Background technique
Heavy metal also brings serious environmental pollution while promoting industrial development, and causes prestige to human health
The side of body.Heavy metal element is unprocessed for some reason to be just discharged into river, lake or ocean, or enters in soil, makes
These rivers, lake, ocean and soil is obtained to be contaminated.Heavy metal can not be degraded, can be in life internal deposition, environment
In heavy metal can by the absorption of animal, plant, marine product etc. and biosphere enrichment eventually enter into human body, make one generate weight
Metal poisoning gently then occurs disease (minamata disease, Itai-itai diseases etc.), and severe one will be dead.Heavy metal can be such that bioprotein loses
It is living, irreversible harm is caused to life entity.Any one can cause the headache of people, dizziness, insomnia, be good in heavy metal
Forget, amentia, arthralgia, calculus, cancer (such as liver cancer, gastric cancer, intestinal cancer, bladder cancer, breast cancer, prostate cancer and black foot
Disease and deformed child) etc., especially to the cell of digestive system, urinary system, internal organs, skin, bone, spirit destroy and be serious.
Therefore heavy metal pollution has become the significant task of environmental monitoring Yu contamination control area research person effectively in Environment control.Lead
It (Pb) is one of higher heavy metal element of toxicity, and the more serious heavy metal element of heavy metal pollution at present, it can be to mind
It causes to damage through system and kidney, can also cause anaemia and cancer.Copper (Cu) is also one of heavy metal element, is accumulated in environment
It is bad that excessive copper will cause crop growth, the harm such as aquatile acute poisoning.
For purification angle, absorption is a kind of mature and efficient mode, and has extensive researching value and good
Good prospect, and one of the main means of Environment control heavy metal pollution at present.The cooperation group of sulfur-containing group is as electronics
Donor acts as highly important effect in the connection of the 8th group 4 transition metal element and other groups.Sulfydryl is to a variety of
Metal ion has very strong selectivity and transfer ability, is good material functional reagent.It has developed at present a variety of
Mercapto-functionalized heavy metal treatment agent, such as mercapto-functionalized magnetic material, mercapto-functionalized nano material, mercapto-functionalized graphite
Alkene/graphene oxide etc..These materials are mostly at high cost, and synthetic method is complicated, some materials still can not in high volume give birth at present
It produces.And above-mentioned material is required to consume a large amount of organic solvents during the preparation process, it is possible to cause secondary pollution to environment.
Flyash is a kind of industrial waste, and yield is huge but utilizes low.It is administered using flyash as adsorbent heavy metal-polluted
The technology of dye has certain development, but the usual highly energy-consuming of technology used at present, uses a large amount of organic solvents.In line with environmental-friendly original
Then, the present invention is using low in cost, environmental pollution is small or does not cause the reagent of environmental pollution, with a kind of energy consumption is low, process is simple
Method prepare mercapto-functionalized flyash, administered for heavy metal in environment, not only can solve a large amount of utilization of fly ash
Difficult problem also has certain social benefit.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of preparation method of mercapto-functionalized flyash and answers
With, being capable of effectively adsorbing heavy metal in water Pb using flyash as the adsorbent of carrier2+、Cu2+Etc. heavy metal ion, obtain water quality
To purification.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of preparation method of mercapto-functionalized flyash, steps are as follows:
(1) flyash is mixed with sulfuric acid solution, 15% sodium hypochlorite is added dropwise, after 25 DEG C of constant temperature are stirred to react 4 hours, used
Distilled water is filtered mixed system and washs to neutrality, and 55 DEG C of drying obtain the flyash of surface hydroxylation；
(2) flyash for the surface hydroxylation that step (1) obtains is dispersed in dehydrated alcohol, (3- mercaptopropyi) front three is added
Oxysilane, 60 DEG C are heated at reflux after reaction 12 hours with distilled water to mixed system filtration washing, until after filtrate clarification, 55
DEG C drying, obtain mercapto-functionalized flyash.
The concentration of sulfuric acid solution is 1mol/L-18 mol/L in the step (1), and 1g flyash needs the body of sulfuric acid solution
Product is 5mL.
It is 3mL that 1g flyash, which needs the volume of 15% sodium hypochlorite, in the step (2).
The mass ratio of (3- mercaptopropyi) trimethoxy silane and flyash is 0.25:1 in the step (2).
Mercapto-functionalized flyash produced by the present invention is repairing the application in heavy metal pollution of water body.
The mercapto-functionalized flyash for repairing heavy metal pollution of water body is at least one heavy metal-polluted water
Using.
Mercapto-functionalized flyash produced by the present invention is containing mercapto functional group and silica matrix, alumina base
The compound of matter.Wherein mercapto-functionalized reagent select (3- mercaptopropyi) trimethoxy silane or other contain the silicon of sulfydryl
Alkane coupling agent.
Beneficial effects of the present invention: 1, flyash is placed in sulfuric acid solution by the present invention stirs, and is added 15% with given pace
Sodium hypochlorite reaction, using dehydrated alcohol as reaction medium after dry washing is dry, using silane coupling agent as modifying agent, through anti-
Sulfhydryl modified flyash is obtained after answering, wash and drying, treated, and flyash has good adsorption effect to heavy metal.2,
Modified substrates are trade wastes, and the treatment of wastes with processes of wastes against one another is conducive to environmental protection and improvement.3, reaction is low using cost of drugs, synthesis
Process energy consumption is low, does not generate pollutant, environmental-friendly.4, adsorbent has good adsorption capacity to various heavy.5, it inhales
Attached dose has good stability, still has good adsorption capacity to be basically unchanged after placing January.
Detailed description of the invention
Fig. 1 is unmodified flyash (a) and mercapto-functionalized flyash (b) infrared spectrogram.
Fig. 2 is unmodified flyash (A) and mercapto-functionalized flyash (B) SEM test result.
Mercapto-functionalized flyash is to Pb under Fig. 3 different acidity2+, Cu2+Absorption property test result.
Mercapto-functionalized flyash is to Pb under Fig. 4 different temperatures2+, Cu2+Absorption property.
Relationship of the mercapto-functionalized flyash of Fig. 5 to two kinds of ionic adsorption effects and ion concentration.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The mercapto-functionalized flyash of the present embodiment the preparation method is as follows:
(1) compound concentration is the sulfuric acid solution 100mL of 1mol/L, and flyash 20g is added, 60mL is added dropwise after mixing evenly
15% sodium hypochlorite, 25 DEG C isothermal reaction 4 hours, mixture is filtered, is washed flyash to neutrality with distilled water,
55 DEG C of drying；
(2) 100mL dehydrated alcohol is added in the flyash of drying, 5g (3- sulfydryl third is added after being uniformly dispersed in system to be mixed
Base) trimethoxy silane, 60 DEG C are heated at reflux reaction 12 hours, and filtering washs solid with distilled water, it is clear to be washed till filtrate
After clear, 55 DEG C of drying are to get to mercapto-functionalized flyash.
Mercapto-functionalized flyash is used for Pb2+And Cu2+Ion is drifted along or through, and (two kinds of ion concentrations are for solution absorption test
500mg/L), test result is detected with ICP-AES.Mercapto-functionalized flyash is to Pb as the result is shown2+The adsorption efficiency of ion reaches
To 95%, to Cu2+Adsorption efficiency reaches 65%.
Embodiment 2
The mercapto-functionalized flyash of the present embodiment the preparation method is as follows:
(1) compound concentration is the sulfuric acid solution 100mL of 5mol/L, and flyash 20g is added, 60mL is added dropwise after mixing evenly
15% sodium hypochlorite, 25 DEG C isothermal reaction 4 hours, mixture is filtered, is washed flyash to neutrality with distilled water,
55 DEG C of drying；
(2) 100mL dehydrated alcohol is added in the flyash of drying, 5g (3- sulfydryl third is added after being uniformly dispersed in system to be mixed
Base) trimethoxy silane, 60 DEG C are heated at reflux reaction 12 hours, and filtering washs solid with distilled water, it is clear to be washed till filtrate
After clear, 55 DEG C of drying are to get to mercapto-functionalized flyash.
Mercapto-functionalized flyash is used for Pb2+And Cu2+Ion is drifted along or through, and (two kinds of ion concentrations are for solution absorption test
500mg/L), test result is detected with ICP-AES.Mercapto-functionalized flyash is to Pb as the result is shown2+The adsorption efficiency of ion reaches
To 99%, to Cu2+Adsorption efficiency reaches 75%.
Embodiment 3
The mercapto-functionalized flyash of the present embodiment the preparation method is as follows:
(1) compound concentration is the sulfuric acid solution 100mL of 10mol/L, and flyash 20g is added, 60mL is added dropwise after mixing evenly
15% sodium hypochlorite, 25 DEG C isothermal reaction 4 hours, mixture is filtered, is washed flyash to neutrality with distilled water,
55 DEG C of drying；
(2) 100mL dehydrated alcohol is added in the flyash of drying, 5g (3- sulfydryl third is added after being uniformly dispersed in system to be mixed
Base) trimethoxy silane, 60 DEG C are heated at reflux reaction 12 hours, and filtering washs solid with distilled water, it is clear to be washed till filtrate
After clear, 55 DEG C of drying are to get to mercapto-functionalized flyash.
Mercapto-functionalized flyash is used for Pb2+And Cu2+Ion is drifted along or through, and (two kinds of ion concentrations are for solution absorption test
500mg/L), test result is detected with ICP-AES.Mercapto-functionalized flyash is to Pb as the result is shown2+The adsorption efficiency of ion reaches
To 95%, to Cu2+Adsorption efficiency reaches 65%.
Embodiment 4
The mercapto-functionalized flyash of the present embodiment the preparation method is as follows:
(1) compound concentration is the sulfuric acid solution 100mL of 15mol/L, and flyash 20g is added, 60mL is added dropwise after mixing evenly
15% sodium hypochlorite, 25 DEG C isothermal reaction 4 hours, mixture is filtered, is washed flyash to neutrality with distilled water,
55 DEG C of drying；
(2) 100mL dehydrated alcohol is added in the flyash of drying, 5g (3- sulfydryl third is added after being uniformly dispersed in system to be mixed
Base) trimethoxy silane, 60 DEG C are heated at reflux reaction 12 hours, and filtering washs solid with distilled water, it is clear to be washed till filtrate
After clear, 55 DEG C of drying are to get to mercapto-functionalized flyash.
Mercapto-functionalized flyash is used for Pb2+And Cu2+Ion is drifted along or through, and (two kinds of ion concentrations are for solution absorption test
500mg/L), test result is detected with ICP-AES.Mercapto-functionalized flyash is to Pb as the result is shown2+The adsorption efficiency of ion reaches
To 97%, to Cu2+Adsorption efficiency reaches 70%.
Embodiment 5
The mercapto-functionalized flyash of the present embodiment the preparation method is as follows:
(1) compound concentration is the sulfuric acid solution 100mL of 18mol/L, and flyash 20g is added, 60mL is added dropwise after mixing evenly
15% sodium, 25 DEG C isothermal reaction 4 hours, mixture is filtered, is washed flyash to neutrality with distilled water, 55 DEG C baking
It is dry；
(2) 100mL dehydrated alcohol is added in the flyash of drying, 5g (3- sulfydryl third is added after being uniformly dispersed in system to be mixed
Base) trimethoxy silane, 60 DEG C are heated at reflux reaction 12 hours, and filtering washs solid with distilled water, it is clear to be washed till filtrate
After clear, 55 DEG C of drying are to get to mercapto-functionalized flyash.
Mercapto-functionalized flyash is used for Pb2+And Cu2+Ion is drifted along or through, and (two kinds of ion concentrations are for solution absorption test
500mg/L), test result is detected with ICP-AES.Mercapto-functionalized flyash is to Pb as the result is shown2+The adsorption efficiency of ion reaches
To 98%, to Cu2+Adsorption efficiency reaches 71%.
Mercapto-functionalized flyash surface texture characterization:
It is infrared to being carried out respectively without modified flyash and the mercapto-functionalized flyash being prepared by 2 method of embodiment
Spectrum test, gained spectrogram is as shown in Figure 1, wherein (a) is unmodified flyash infrared spectrogram, (b) to be mercapto-functionalized
Flyash infrared spectrogram.From figure 1 it appears that in 3437cm-1Place is Si-OH stretching vibration and CFA-SH adsorption
The infrared light spectral peak of water, 2922cm-1It is-CH3Stretching vibration peak, 2848cm-1It is-CH2Symmetrical stretching vibration peak, 1626cm-1It is
Si-OH flexural vibrations peak, 1090cm-1It is Si-O-Si asymmetric stretch vibration peak.912 cm-1It is Si-C key infrared light spectral peak.
The bimodal of sulfydryl respectively appears in 2321cm-1And 2286cm-1Place, this two peak is in mercapto-functionalized flyash infrared spectrogram (b)
Middle appearance, and do not occur in unmodified flyash infrared spectrogram (a), it was demonstrated that successfully sulfydryl is grafted to according to embodiment 2
Fine coal gray surface.
To without modified flyash and the mercapto-functionalized flyash being prepared according to 2 statement methods of embodiment
SEM test is carried out, test results are shown in figure 2, wherein (A) is unmodified flyash, (B) is stated according to embodiment 2
The mercapto-functionalized flyash that method is prepared.From figure 2 it can be seen that mercapto-functionalized flyash is compared to unmodified function
Flyash can be changed with more tiny and more uniform microstructure, this makes mercapto-functionalized flyash have bigger ratio
Surface area, this facilitates raising of the mercapto-functionalized flyash to heavy metal ion adsorbed effect.
Embodiment 6
Mercapto-functionalized flyash is to Pb under different acidity2+, Cu2+Absorption property test: 100mg/L Pb (NO is prepared respectively3)2
Solution and CuCl2Solution 20mL, every kind of solution take 8 parts, adjust pH range at every part of 3-10(with 0.1M ammonium hydroxide and 0.1M dust technology
The pH error of solution is no more than ± 0.05), each 1g CFA-SH that is added takes supernatant after 298K shakes 2 hours after centrifugation, use
ICP-AES tests Cu2+ , Pb2+Concentration.Test result is done into figure to pH with adsorption efficiency T % and obtains Fig. 3.It can from figure
Out, when the ph is lower, since hydrionic absorption competition acts on, mercapto-functionalized flyash is for Pb2+And Cu2+Absorption effect
Fruit is undesirable.When pH rises to 5-6, mercapto-functionalized flyash has obvious rising to the adsorption effect of two kinds of ions.When
PH is more than after 7, and mercapto-functionalized flyash tends towards stability to the adsorption effect of two kinds of ions and adsorption effect is good.
Embodiment 7
Mercapto-functionalized flyash is to Pb under different temperatures2+, Cu2+The test of absorption property: compound concentration 100mg/L,
Pb (the NO of 200mg/L, 500mg/L, 1000mg/L, 2000mg/L3)2Solution and CuCl2Solution, every kind of solution take 20mL, are added
The mercapto-functionalized flyash that 1g is prepared according to embodiment 1, after being shaken 2 hours at 15 DEG C, 35 DEG C and 55 DEG C respectively from
The heart takes supernatant, with Cu in ICP-AES detection supernatant2+And Pb2+Concentration.By the pass of two kinds of ionic adsorption effects and temperature
Figure does in system, as shown in figure 4, being Pb2+Adsorption effect curve and Cu2+Adsorption effect curve.It can be seen from the figure that higher temperature
Degree and lower temperature have an adverse effect to the absorption property of mercapto-functionalized flyash, but under usual temperature, sulfydryl
Functionalization flyash has preferable adsorption effect for two kinds of ions, and adsorption effect is more steady in shown concentration range
It is fixed.
Embodiment 8
Mercapto-functionalized flyash is to Pb under various concentration2+, Cu2+The test of absorption property: compound concentration 100mg/L,
Pb (the NO of 200mg/L, 500mg/L, 1000mg/L, 2000mg/L3)2Solution and CuCl2Solution, every kind of solution take 20mL, are added
The mercapto-functionalized flyash that 1g is prepared according to embodiment 2, centrifuging and taking supernatant after shaking 2 hours at 25 DEG C are used
ICP-AES detects Cu in supernatant2+And Pb2+Concentration.Mercapto-functionalized flyash is dense to two kinds of ionic adsorption effects and ion
The relationship of degree is as shown in Figure 5.It can be seen from the figure that with the increase of ion concentration, mercapto-functionalized flyash to two kinds from
The saturated extent of adsorption of son is also gradually increased, and is illustrated in the ion concentration range studied, mercapto-functionalized flyash is to two kinds
Ion has preferable adsorption effect.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (6)
1. a kind of preparation method of mercapto-functionalized flyash, it is characterised in that steps are as follows:
(1) flyash is mixed with sulfuric acid solution, 15% sodium hypochlorite is added dropwise, after 25 DEG C of constant temperature are stirred to react 4 hours, used
Distilled water is filtered mixed system and washs to neutrality, and 55 DEG C of drying obtain the flyash of surface hydroxylation；
(2) flyash for the surface hydroxylation that step (1) obtains is dispersed in dehydrated alcohol, (3- mercaptopropyi) front three is added
Oxysilane, 60 DEG C are heated at reflux after reaction 12 hours with distilled water to mixed system filtration washing, until after filtrate clarification, 55
DEG C drying, obtain mercapto-functionalized flyash.
2. the preparation method of mercapto-functionalized flyash according to claim 1, it is characterised in that: in the step (1)
The concentration of sulfuric acid solution is 1mol/L-18 mol/L, and it is 5mL that 1g flyash, which needs the volume of sulfuric acid solution,.
3. the preparation method of mercapto-functionalized flyash according to claim 1, it is characterised in that: in the step (2)
It is 3mL that 1g flyash, which needs the volume of 15% sodium hypochlorite,.
4. the preparation method of mercapto-functionalized flyash according to claim 1, it is characterised in that: in the step (2)
The mass ratio of (3- mercaptopropyi) trimethoxy silane and flyash is 0.25:1.
5. mercapto-functionalized flyash made from -4 preparation method is in repairing heavy metal pollution of water body according to claim 1
Using.
6. application according to claim 6, it is characterised in that: the mercapto-functionalized powder for repairing heavy metal pollution of water body
Application of the coal ash at least one heavy metal-polluted water.
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| CN113304734A (en) * | 2021-06-04 | 2021-08-27 | 辽宁工程技术大学 | Preparation method, product and application of modified lignite |
| CN114762822A (en) * | 2021-01-13 | 2022-07-19 | 神华神东煤炭集团有限责任公司 | Composite adsorption membrane for water treatment and preparation method and application thereof |
| CN115554977A (en) * | 2022-11-08 | 2023-01-03 | 陕西矸山翠环保科技有限公司 | Novel adsorbent for dye and heavy metal pollution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114762822A (en) * | 2021-01-13 | 2022-07-19 | 神华神东煤炭集团有限责任公司 | Composite adsorption membrane for water treatment and preparation method and application thereof |
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| CN115554977A (en) * | 2022-11-08 | 2023-01-03 | 陕西矸山翠环保科技有限公司 | Novel adsorbent for dye and heavy metal pollution |
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