CN104826588A - Preparation and regeneration method of fluorine removing material on basis of coal-based coke powder - Google Patents
Preparation and regeneration method of fluorine removing material on basis of coal-based coke powder Download PDFInfo
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Abstract
The invention discloses a preparation and regeneration method of a fluorine removing material on the basis of coal-based coke powder. The coal-based coke powder is the byproduct in the coking industry. The preparation method comprises steps of coal-based coke powder pre-oxidation and activation, preparation of precursor powder containing active fluorine-removing components, preparation and carbonization of precursor particles, and post-treatment of carbonized particles. The regeneration of the fluorine removing material comprises a step of soaking the fluorine removing material with a saturated adsorbing capacity in a caustic alkali solution and an aluminum sulfate or iron sulfate solution in sequence. The provided composite fluorine removing material can efficiently remove the fluorine in common industrial wastewater, especially the zinc sulfate electrolyte in zinc hydrometallurgy; and has the characteristics of great amount of removed fluorine, rapidness, low cost, and recyclable property.
Description
Technical field
The present invention relates to coking industry byproduct---the application technology as the second resource of coal-based coke powder, be specifically related to the preparation of a kind of defluorination material based on coal-based coke powder and renovation process, this defluorination material efficiently can remove the fluorine in commonly industrial wastewater, obvious to the removal effect of fluorine in zinc sulphate electrolyte in zinc hydrometallurgy especially.Belong to material for water treatment preparing technical field.
Background technology
The industry of China fluorine chemistry, iron and steel are produced, aluminium electroloysis and aluminium is processed, relieving haperacidity and sulphuric fertilizer is produced, glassware manufacture and the industry such as processing, non-ferrous metal metallurgy all produce a large amount of fluoride wastes every year, meanwhile, the also severe overweight of the Oil repellent in the surface and ground water of certain areas.The existence of high fluorine in water body, causes great harm to the production of the mankind, living environment.
In order to reduce the harm of fluorine, be developed multiple technology of Fluoride Removal, these technology mainly comprise coagulant sedimentation, absorption method, ion-exchange and membrane separation process etc.Although these technology have positive effect in reduction Fluoride Concentration In Waters, the defect still have that processing cost is high, defluorinating agent preparation needs to consume more resource, defluorinating agent consumption is large, producing secondary pollution, the process of different PH water body is not had to the aspects such as universality.Patent CN102259946A, CN102357357A and CN104324684A all can obtain good defluorination effect, but have employed the raw material containing elements such as Ti, Zr, Ce, cause the cost of these defluorination materials high, and are only applicable to process neutral water; Patent CN1966407A discloses aluminium salt and phosphate removes the method for fluorine to acidic zinc electrolyte, but this method result in the not small loss of valuable element zinc in electrolyte.
On the other hand, China is a coke production big country, because the granularity of coke powder is too little, fixed carbon content in coke powder is lower, at present except small part is utilized as leaning agent, major part is all in idle state, and this not only needs certain stockyard to place coke powder thus to result in taking of a large amount of land resource, but also may produce pollution to environment.
Summary of the invention
The object of the present invention is to provide a kind of process simple, easy to operate, with coking industry accessory substance---coal-based coke powder is the preparation of the defluorination material based on coal-based coke powder and the renovation process of primary raw material; Defluorination material prepared by the present invention not only can realize the efficient removal of fluorine in wide pH value scope water body, but also the coal-based coke powder of recycling.
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, comprises the steps:
The first step: the pre-oxidation treatment of coal-based coke powder
After coal-based coke powder particle mean size being less than or equal to 20um mixes with pre-oxidation agent, the water adding coal-based coke powder same volume is made into slip, and slip is after 400-600 DEG C of insulation 1-2h, and cooling, obtains pre-oxidation coal-based coke powder naturally;
Second step: the activation process of the coal-based coke powder of pre-oxidation
Coal-based for pre-oxidation coke powder is warming up to 750-900 DEG C under inert gas shielding, passes into steam 90-180min, after cooling to room temperature with the furnace, be washed to washing lotion pH value and be less than or equal to 9, obtain activating coal-based coke powder;
Or after being mixed by coal-based to caustic alkali and pre-oxidation coke powder, mixture is warming up to 700-850 DEG C, insulation 60-120min, is washed to washing lotion pH value and is less than or equal to 9, obtain activating coal-based coke powder;
3rd step: prepared by precursor powder
Coal-based for activation prepared by second step coke powder is added in soluble magnesium, aluminum salt solution by liquid-solid ratio 1:1 ~ 5:1, stir 30min-120min, filter after with slow release precipitator solution ph being adjusted to 6.8-7.5, filter cake is broken up after drying at 100 ~ 120 DEG C, obtains precursor powder;
In described soluble magnesium, aluminum salt solution, aluminium ion and magnesium ion mol ratio are 1:1 ~ 10:1, and magnesium ion and aluminum ions molar concentration sum are 1mol/L ~ 10mol/L;
4th step: prepared by granular precursor
Get the 3rd step gained precursor powder, interpolation accounts for the bonding binder of got precursor quality 10-30% and stirs, and causes the spheric granules of 0.5-3.5mm, in 40-60 DEG C of dry more than 24h, obtains granular precursor;
Described bonding binder is in the organic carbon source solution of 30-50% in mass percentage concentration, adds the powdery pore forming material accounting for organic carbon source quality 5-10%, stir, obtain;
5th step: the charing of granular precursor
The granular precursor 4th step obtained, under inert protective atmosphere, is heated to 200-400 DEG C, after constant temperature 1-5h, continues to be heated to 600-800 DEG C, constant temperature 2-6h, with stove cooling, obtains carbonizing particle;
6th step: the post processing of charing particle
Filter after 5th step gained charing particle is placed in aftertreatment fluid dipping, filter residue dries in the shade naturally, obtains the defluorination material based on coal-based coke powder.
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, in the first step, in slip, the quality of pre-oxidation agent accounts for the 10-20wt% of coal-based coke powder quality; Described pre-oxidation agent is selected from potassium nitrate and/or potassium permanganate, and potassium nitrate mixes with arbitrary proportion with potassium permanganate.
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, in second step, activation process programming rate is 5-10 DEG C/min.
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, in second step, described caustic alkali be selected from NaOH or potassium hydroxide any one; The addition of caustic alkali is 2-5 times of the coal-based coke powder weight of pre-oxidation.
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, soluble magnesium, aluminium salt described in the 3rd step, refer in sulfate that cation is magnesium or aluminium, nitrate, chlorate any one;
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, described in the 3rd step, slow release precipitator is selected from any one in urea and carbon ammonium;
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, described in the 4th step, organic carbon source refers to the one in phenolic resins, Lauxite, melamine formaldehyde resin, epoxy resin, unsaturated-resin, polyurethane, polyimides; One in the solvent selected from methanol in dissolved organic carbon source, ethanol, acetone, n-hexane; Powdery pore forming material refers to urea or the carbon ammonium that granularity is less than 1um.
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, the first step and the inert protective atmosphere described in the 5th step are selected from least one in ammonia, nitrogen, hydrogen, argon gas.
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, in the 5th step, the charing of granular precursor, first, with the programming rate of 1-10 DEG C/min, is heated to 200-400 DEG C, then, is heated to 600-800 DEG C with the programming rate of 1-5 DEG C/min.
A kind of defluorination material preparation method based on coal-based coke powder of the present invention, described in the 6th step, aftertreatment fluid refers to the one in ferrum sulfuricum oxydatum solutum or aluminum sulfate solution, and the concentration range of ferrum sulfuricum oxydatum solutum or aluminum sulfate solution is 2-4%; Charing particle is placed in aftertreatment fluid and floods 3-6h.The renovation process of a kind of defluorination material based on coal-based coke powder of the present invention, that defluorination material after Adsorption of fluoride amount being reached capacity first is placed in the NaOH of concentration 1-3% or potassium hydroxide solution soaks 6-12h, and then defluorination material is placed in the ferrum sulfuricum oxydatum solutum of concentration 2-4% or aluminum sulfate solution soaks 6-12 hour, realize the regeneration of defluorination material.
Compared with existing known technology of Fluoride Removal, the present invention has following advantages and good effect:
(1) with the coal-based coke powder of the accessory substance of coking industry for defluorination material prepared by raw material, facilitate on the one hand the recycling of coal-based coke powder, ensure that the low cost preparation of defluorination material of the present invention on the other hand;
(2) pre-oxidation to coal-based coke powder and activation process is passed through, make to create abundant hole in coal-based coke powder particle, these holes are provided with good fluorine adsorption function on the one hand, can make on the other hand to have that good fluorine removes the magnesium of function, aluminium active component is evenly distributed in coke powder matrix, be conducive to obtaining defluorination effect fast;
The thermosetting resin (phenolic resins, Lauxite, melamine formaldehyde resin etc.) adopted in (3) the 4th step bonding binders and labile pore forming material (urea and carbon ammonium), on the one hand, ensure that the integrality of defluorination material particle prepared by the present invention, and the activity containing magnalium can not be run off easily except fluorine component from defluorination material, thus extend the service life of defluorination material; On the other hand, thermosetting resin charing and the decomposition of pore forming material have impelled except fluorine granular material surface produces a large amount of holes, this increases not only the specific area of defluorination material, ensure that carrying out fast except fluorine process, and these holes also help in adsorption-defluorination process a large amount of gelatinous precipitates produced, thus make the separating property between defluorination material and water body good, avoid the appearance of the phenomenons such as the technology such as tradition flocculation easily harden.
(4) defluorination material provided by the present invention can be used by straightforward procedure regeneration, and regeneration process can reduce the use cost of defluorination material further; In addition, after defluorination material is entirely ineffective, because bulk composition is wherein carbon, it can use as fuel, can not cause secondary pollution.
(5) present invention process method is simple, easy to operate, prepared defluorination material have fluoride removing quantity large, except fluorine speed feature fast.
Accompanying drawing explanation
Accompanying drawing 1 is the SEM photo of coal-based coke powder.
Accompanying drawing 2 is the SEM photo by coke powder coal-based after pre-oxidation and activation process in embodiment 1.
Comparison diagram 1 is known with Fig. 2, and pre-oxidation and activation process make the surface of coal-based coke powder create a large amount of holes.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited thereto.
Embodiment 1
With the preparation of the defluorination material of steam activation coke powder and regeneration thereof
(1) defluorination material is prepared
The first step: the pre-oxidation treatment of coal-based coke powder
The pre-oxidation agent potassium nitrate being about to the coal-based coke powder and coal-based coke powder quality 20wt% being crushed to below 20um mixes, and the water adding coal-based coke powder same volume is made into slip, slip is placed in after high temperature furnace is incubated 2h at 400 DEG C, naturally cools, namely obtains the coal-based coke powder of pre-oxidation.
Second step: the activation process of the coal-based coke powder of pre-oxidation
Coal-based for pre-oxidation treatment gained coke powder is warming up to 750 DEG C under nitrogen protection, with the speed of 5 DEG C/min, then passes into steam 90min at this temperature, afterwards under nitrogen protection with stove cooling, washing makes its pH value be less than 9, namely obtains activating coal-based coke powder;
3rd step: prepared by precursor powder
First, preparation is containing magnesium ion and aluminum ions solution.Take soluble magnesium, aluminium salt by aluminium ion and magnesium ion mol ratio 10:1, and be dissolved in water by these two kinds of salt and make salting liquid, in solution, magnesium ion and aluminum ions molar concentration sum are 10mol/L.
Then, adding in above-mentioned salting liquid by activating coal-based coke powder prepared by second step by liquid-solid ratio 3:1, stirring 120min, filter after with slow release precipitator solution pH value being adjusted to 6.8-7.5, filter cake dries more than 12h at 100 DEG C, dries after filter cake is broken up and namely obtains precursor powder.
4th step: prepared by granular precursor
First preparation bonding binder.By phenol formaldehyde resin dissolves in acetone solvent, be mixed with the acetone organic solution of concentration 30%, then the urea accounting for organic carbon source quality 5%, granularity is less than 1um is added in organic solution when stirring, namely obtain the binder that bonds;
Then, get the 3rd step gained precursor powder, interpolation accounts for the bonding binder of got precursor quality 30% and stirs, and causes the spheric granules of 0.5-3.5mm, in 40 DEG C of dry 24h, namely obtains granular precursor;
5th step: the charing of granular precursor
By gained granular precursor in the 4th step under inert protective atmosphere, first by the programming rate of 1 DEG C/min, be heated to 200 DEG C, constant temperature 5h, be then heated to 600 DEG C by the programming rate of 5 DEG C/min, with stove cooling after constant temperature 2h, namely obtain carbonizing particle;
6th step: the post processing of charing particle
The ferrum sulfuricum oxydatum solutum that 4th step gained charing particle is placed in concentration 3% is flooded 3h, naturally dries in the shade after then filtering, namely obtain defluorination material of the present invention.
(2) result of use of defluorination material prepared by the present embodiment:
1. the defluorination effect in the fluorine-containing water body of centering
First time is except fluorine experiment: get defluorination material 5g prepared by the present embodiment, drop in the neutral water body of 100ml pH value about 7, fluorinated volume 30mg/l, and filter after stirring 20min, test finds, fluorinated volume in filtrate in water body has been down to 0.5mg/l, and filter residue continues process next group fluoride waste;
Second time is except fluorine experiment: dropped in the water body of the same fluorinated volume of 100ml except gained after fluorine process filters filter residue first time, and find after stirring 30min that the Oil repellent in filtrate is down to 0.5mg/l;
Repeat above-mentioned except after fluorine process 20 times, the Oil repellent in gained filtrate is about 5mg/l.
Fluorine in defluorination material centering water body prepared by visible the present embodiment has the removal effect of the degree of depth, and it is very fast to remove speed.
2. to the defluorination effect in fluorine-containing zinc electrolyte
Be that the zinc sulfate leaching liquid of 85mg/L is as removing fluorine stoste with Funing tablet, getting 1kg defluorination material puts in 1 cube of stoste, at the temperature of 38 DEG C, filters after mechanical agitation 1h, get filtrate detection and find that wherein fluorinion concentration is down to 3.5mg/l, filter residue continues the fluorine-containing electrolyte of process next group.
Filter residue is continued process 15 cubes of electrolyte (each 1 cube) in batches to find afterwards, in electrolyte, fluorinated volume is down to 25mg/L.
After removing fluorine process 16 times, the zinc loss in electrolyte is less than 2%.
(3) regeneration of defluorination material
The sodium hydroxide solution that the defluorination material above-mentioned process being crossed neutral fluorine-containing water body and electrolyte is placed in concentration 1% soaks 12h, and then aluminum sulfate solution defluorination material being placed in concentration 2.5% soaks 6 hours, namely achieves the regeneration of defluorination material.The defluorination material regenerated after 2 times has the same effect just preparing defluorination material.
Embodiment 2
With the preparation of the defluorination material of activation of potassium hydroxide coke powder and regeneration thereof
(1) defluorination material is prepared
The first step: the pre-oxidation treatment of coal-based coke powder
The potassium permanganate being about to the coal-based coke powder and coal-based coke powder quality 20wt% being crushed to below 20um mixes, and the water adding coal-based coke powder same volume is made into slip, slip is placed in after high temperature furnace is incubated 1h at 600 DEG C, naturally cools, namely obtains the coal-based coke powder of pre-oxidation.
Second step: the activation process of the coal-based coke powder of pre-oxidation
Mixed with the coal-based coke powder of pre-oxidation by the potassium hydroxide of 5 times of pre-oxidation coal-based coke powder weight, after then mixture being warming up to 750 DEG C by the speed of 5 DEG C/min, be incubated 60min, washing makes its pH value be less than 9, obtains activating coal-based coke powder.
3rd step: prepared by precursor powder
First, preparation is containing magnesium ion and aluminum ions solution.Take soluble magnesium, aluminium salt by aluminium ion and magnesium ion mol ratio 1:1, and be dissolved in water by these two kinds of salt and make salting liquid, in solution, magnesium ion and aluminum ions molar concentration sum are 1mol/L.
Then, adding in above-mentioned salting liquid by activating coal-based coke powder prepared by second step by liquid-solid ratio 5:1, stirring 30min, filter after with slow release precipitator solution pH value being adjusted to 6.8-7.5, filter cake dries more than 12h at 100 ~ 120 DEG C, dries after filter cake is broken up and namely obtains precursor powder.
4th step: prepared by granular precursor
First preparation bonding binder.Dissolve in ethanol by Lauxite, be mixed with the resin solution of concentration 50%, then the carbon ammonium accounting for resin quality 10%, granularity is less than 1um is added in organic solution when stirring, namely obtain the binder that bonds;
Then, get the 3rd step gained precursor powder, interpolation accounts for the bonding binder of got precursor quality 30% and stirs, and causes the spheric granules of 0.5-3.5mm, in 60 DEG C of dry more than 24h, namely obtains granular precursor;
5th step: the charing of granular precursor
By gained granular precursor in the 4th step under inert protective atmosphere, first by the programming rate of 10 DEG C/min, be heated to 400 DEG C, constant temperature 1h, be then heated to 800 DEG C by the programming rate of 1 DEG C/min, with stove cooling after constant temperature 2h, namely obtain carbonizing particle;
6th step: the post processing of charing particle
4th step gained charing particle is placed in aftertreatment fluid and floods 3-6h, naturally dry in the shade after then filtering, namely obtain defluorination material of the present invention.
The aluminum sulfate solution that 4th step gained charing particle is placed in concentration 2.5% is flooded 6h, naturally dries in the shade after then filtering, namely obtain defluorination material of the present invention.
(2) result of use of defluorination material prepared by the present embodiment:
By defluorination material 5g prepared by the present embodiment, drop in the zinc sulphate electrolyte of 100ml pH value about 5, fluorinated volume 285mg/l, and filter after stirring 30min, test finds that the fluorinated volume in electrolyte has been down to 8.6mg/l;
Second time is except fluorine experiment: dropped in the electrolyte of the same fluorinated volume of 100ml except gained after fluorine process filters filter residue first time, and find after stirring 30min that the Oil repellent in filtrate is down to 12mg/l;
Repeat that above-mentioned Oil repellent in gained filtrate is about 42mg/l except after fluorine process 12 times, still can reach electrolysis requirement (usually require fluorinated volume lower than 50mg/l) in electrolyte.
After removing fluorine process 12 times, the zinc loss in electrolyte is less than 2%.
Prepared by visible the present embodiment, defluorination material has degree of depth removal effect to the fluorine in acidic electrolysis bath, and it is very fast to remove speed, and in addition, this defluorination material significantly can not reduce the valuable metal content in electrolyte.
(3) regeneration of defluorination material
The potassium hydroxide solution that the above-mentioned defluorination material processing electrolyte is placed in concentration 3% is soaked 6h, and then ferrum sulfuricum oxydatum solutum defluorination material being placed in concentration 3% soaks 6 hours, namely achieves the regeneration of defluorination material.The defluorination material regenerated after 2 times has the same effect just preparing defluorination material.
Claims (10)
1., based on a defluorination material preparation method for coal-based coke powder, comprise the steps:
The first step: the pre-oxidation treatment of coal-based coke powder
After coal-based coke powder particle mean size being less than or equal to 20um mixes with pre-oxidation agent, the water adding coal-based coke powder same volume is made into slip, and slip is after 400-600 DEG C of insulation 1-2h, and cooling, obtains pre-oxidation coal-based coke powder naturally;
Second step: the activation process of the coal-based coke powder of pre-oxidation
Coal-based for pre-oxidation coke powder is warming up to 750-900 DEG C under inert gas shielding, passes into steam 90-180min, after cooling to room temperature with the furnace, be washed to washing lotion pH value and be less than or equal to 9, obtain activating coal-based coke powder;
Or after being mixed by coal-based to caustic alkali and pre-oxidation coke powder, mixture is warming up to 700-850 DEG C, insulation 60-120min, is washed to washing lotion pH value and is less than or equal to 9, obtain activating coal-based coke powder;
3rd step: prepared by precursor powder
Coal-based for activation prepared by second step coke powder is added in soluble magnesium, aluminum salt solution by liquid-solid ratio 1:1 ~ 5:1, stir 30min-120min, filter after with slow release precipitator solution ph being adjusted to 6.8-7.5, filter cake is broken up after drying at 100 ~ 120 DEG C, obtains precursor powder;
In described soluble magnesium, aluminum salt solution, aluminium ion and magnesium ion mol ratio are 1:1 ~ 10:1, and magnesium ion and aluminum ions molar concentration sum are 1mol/L ~ 10mol/L;
4th step: prepared by granular precursor
Get the 3rd step gained precursor powder, interpolation accounts for the bonding binder of got precursor quality 10-30% and stirs, and causes the spheric granules of 0.5-3.5mm, in 40-60 DEG C of dry more than 24h, obtains granular precursor;
Described bonding binder is in the organic carbon source solution of 30-50% in mass percentage concentration, adds the powdery pore forming material accounting for organic carbon source quality 5-10%, stir, obtain;
5th step: the charing of granular precursor
The granular precursor 4th step obtained, under inert protective atmosphere, is heated to 200-400 DEG C, after constant temperature 1-5h, continues to be heated to 600-800 DEG C, constant temperature 2-6h, with stove cooling, obtains carbonizing particle;
6th step: the post processing of charing particle
Filter after 5th step gained charing particle is placed in aftertreatment fluid dipping, filter residue dries in the shade naturally, obtains the defluorination material based on coal-based coke powder.
2. a kind of defluorination material preparation method based on coal-based coke powder according to claim 1, it is characterized in that: in the first step, in slip, the quality of pre-oxidation agent accounts for the 10-20wt% of coal-based coke powder quality; Described pre-oxidation agent is selected from potassium nitrate and/or potassium permanganate.
3. a kind of defluorination material preparation method based on coal-based coke powder according to claim 1, it is characterized in that: in second step, activation process programming rate is 5-10 DEG C/min.
4. a kind of defluorination material preparation method based on coal-based coke powder according to claim 1, is characterized in that: in second step, described caustic alkali be selected from NaOH or potassium hydroxide any one; The addition of caustic alkali is 2-5 times of the coal-based coke powder weight of pre-oxidation.
5. a kind of defluorination material preparation method based on coal-based coke powder according to claim 1, is characterized in that: soluble magnesium, aluminium salt described in the 3rd step, refers to any one in sulfate that cation is magnesium or aluminium, nitrate, chlorate.
6. a kind of defluorination material preparation method based on coal-based coke powder according to claim 1, is characterized in that: described in the 3rd step, slow release precipitator is selected from any one in urea and carbon ammonium.
7. a kind of defluorination material preparation method based on coal-based coke powder according to claim 1, is characterized in that: described in the 4th step, organic carbon source refers to the one in phenolic resins, Lauxite, melamine formaldehyde resin, epoxy resin, unsaturated-resin, polyurethane, polyimides; One in the solvent selected from methanol of organic carbon source solution, ethanol, acetone, n-hexane; Powdery pore forming material refers to urea or the carbon ammonium that granularity is less than 1um.
8. a kind of defluorination material preparation method based on coal-based coke powder according to claim 1, is characterized in that: in the 5th step, the charing of granular precursor, first, with the programming rate of 1-10 DEG C/min, 200-400 DEG C is heated to, then, 600-800 DEG C is heated to the programming rate of 1-5 DEG C/min.
9. a kind of defluorination material preparation method based on coal-based coke powder according to claim 1-8 any one, it is characterized in that: described in the 6th step, aftertreatment fluid refers to the one in ferrum sulfuricum oxydatum solutum or aluminum sulfate solution, the concentration range of ferrum sulfuricum oxydatum solutum or aluminum sulfate solution is 2-4%; Charing particle is placed in aftertreatment fluid and floods 3-6h.
10. the renovation process based on the defluorination material of coal-based coke powder, that defluorination material after Adsorption of fluoride amount being reached capacity first is placed in the NaOH of concentration 1-3% or potassium hydroxide solution soaks 6-12h, and then defluorination material is placed in the ferrum sulfuricum oxydatum solutum of concentration 2-4% or aluminum sulfate solution soaks 6-12 hour, realize the regeneration of defluorination material.
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| CN108993382A (en) * | 2018-06-25 | 2018-12-14 | 湖南烯富环保科技有限公司 | A kind of defluorination material and its regeneration method based on bacteria residue |
| CN113117643A (en) * | 2021-01-07 | 2021-07-16 | 河南省高新技术实业有限公司 | Modified biomass charcoal adsorption material, preparation method and application thereof, and method for regenerating modified biomass charcoal adsorption material |
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| SNEHA JAGTAP ET AL.: "Fluoride in Drinking Water and Defluoridation of Water", 《CHEMICAL REVIEWS》 * |
| 田宇红等: "焦粉活性炭的制备及应用研究进展", 《煤炭技术》 * |
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| CN106179180A (en) * | 2016-09-18 | 2016-12-07 | 中南大学 | A kind of solution of zinc sulfate defluorination material and preparation method |
| CN106179180B (en) * | 2016-09-18 | 2019-02-05 | 中南大学 | A kind of solution of zinc sulfate defluorination material and preparation method |
| CN108993382A (en) * | 2018-06-25 | 2018-12-14 | 湖南烯富环保科技有限公司 | A kind of defluorination material and its regeneration method based on bacteria residue |
| CN108993382B (en) * | 2018-06-25 | 2021-09-07 | 湖南烯富环保科技有限公司 | Defluorination material based on mushroom dregs and regeneration method thereof |
| CN113117643A (en) * | 2021-01-07 | 2021-07-16 | 河南省高新技术实业有限公司 | Modified biomass charcoal adsorption material, preparation method and application thereof, and method for regenerating modified biomass charcoal adsorption material |
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