CN108905989A - A kind of preparation method and application of defluorination material - Google Patents
A kind of preparation method and application of defluorination material Download PDFInfo
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- CN108905989A CN108905989A CN201810857159.3A CN201810857159A CN108905989A CN 108905989 A CN108905989 A CN 108905989A CN 201810857159 A CN201810857159 A CN 201810857159A CN 108905989 A CN108905989 A CN 108905989A
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
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Abstract
The invention discloses a kind of preparation methods of defluorination material, reed stem is gone after soil to clean to air-dry and pulverize and sieve by this method, then acid solution is added and is heated to reflux progress acidolysis desugar, acidolysis residue is obtained through being separated by solid-liquid separation again, and it is dried after being rinsed with deionized water to neutrality, acidolysis residue after drying is finally subjected to expanding treatment, obtains defluorination material.The invention also discloses a kind of method for removing fluorine ion in water removal using defluorination material, defluorination material is first added in fluoride waste and stirs to get mixed liquor and stand by this method, and inorganic flocculating agent is then added and stands, be eventually adding flocculation aid and stand.The present invention carries out expanding treatment to the reed stem after desugar, considerably increases the surface area of defluorination material, and increase the fluorine adsorption site in defluorination material, improves the fluorine adsorbance of defluorination material.Present invention application defluorination material removes fluorine ion in water removal, further enhances defluorination effect, and bad residual is few, environmentally protective.
Description
Technical field
The invention belongs to water-treatment technology fields, and in particular to a kind of preparation method and application of defluorination material.
Background technique
Fluorine element is one of halogen and the essential trace elements of the human body common in nature.A small amount of fluorine from
Son is beneficial to human body, but when fluorine ion mass concentration is greater than 1.5mg/L will bring detrimental effect to human body, and right
Plant can also generate toxic action.Known according to investigations, 80% fluorine ion can directly be absorbed by the body in water body, and drinking water
It is the main source of required fluorine ion to be provided for the mankind, therefore the removal of fluoride ion in drinking water has attracted people's attention.
China《Drinking water standard》It provides, the fluorine content in drinking water should be in 1.0mg/L or less.
The main methods of fluoride waste have chemical precipitation method, electrocoagulation, absorption method and flocculence at present.Chemistry is heavy
Shallow lake method is common defluorination method, and easy to operate, expense is low, but slowly and after processing fluorinion concentration reaches generation sediment
Less than national requirements.Electrocoagulation is a kind of novel technology of Fluoride Removal, suitable for the fluoride waste of low concentration, principle and Coagulation Method
Identical, the body refuse amount of this method is few, but electrode is easy passivation, and power consumption is caused to increase.The principle of flocculence is flocculant hydrolysis
Cation absorption fluorine ion and mutually aggregation become biggish floccule and precipitate, achieve the effect that fluorine removal, suitable for fluorinated volume
Lower waste water.Absorption method is a kind of most method of China's application study, has easy to operate, and it is excellent that at low cost and effect is good etc.
Point, suitable for the waste water of low concentration, most common adsorbent is aluminium salt, but there are problems that aluminium residual.Xie Hong et al. has studied
The Fluoride-Absorption Capacity of activated alumina, the results showed that activated alumina has good defluorination effect, but can remain in water a large amount of
Activated aluminum, Al3+Residual quantity conference causes damages to environment, can also have damage to human body, and more serious person will cause people's dementia and (thank
The Fluoride-Absorption Capacity of rainbow, the rigid Defluorination of Formation Mater By Adsorption On Activated Alumina agent of Jia Wenbo, Wu Zhi studies Central China University of Science and Technology journal (medicine) [J],
2005,34 (5):644-646.).Handsome et al. the method mixed using aluminium salt and clay is contained come fluorine removal, defluorination effect significantly improves,
But the treatment effect of clay is limited, and the presence of still active aluminium (contains the research ring of fluorine ion in handsome adsorption by clay water
Border science guide [J], 2008,27 (4):7-8.).Jiang Shuanying et al., which has studied, removes removing fluorine in water with clay and natural flocculating agent MR
Ion, it is also harmless to human body since natural flocculating agent MR is nontoxic, and the presence of activated aluminum is effectively reduced, but this flocculation
Agent is at high cost, and production is complicated and is not easy to obtain, and influencing its popularization and application in remote districts and rural area, (Jiang Shuanying, high court of a feudal ruler credit are viscous
Research chemical industry environmental protection [J] of the soil to fluorine ion Adsorption mechanism in water, 2003,23 (4):204-208.).
The plant being widely present in natural environment is a kind of cheap, reproducible natural adsorbent material, and reed belongs to more
Year aquatic class plant, to maintaining the ecosystem stable and removal pollutant plays an important role.So far, using reed as raw material
Defluorination material is prepared to be rarely reported.Xu Haiyang et al. prepares defluorinating agent, fluorine removal effect with HCl acidolysis desugar to the root, stem, leaf of reed
Fruit is significant, and wherein the defluorination effect of root is best, but the root of reed is difficult to obtain in practical applications, and relative to stem, Ye Lai
The amount of saying is few, and again without other optimization techniques after acidolysis desugar, defluorination effect is limited (in Xu Haiyang reed residuum adsorbed water body
The performance study [D] of fluorine ion, Chang An University, 2017.).
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of defluorination material
Preparation method.The preparation method is pressurized the reed stem after desugar using pressure-air, then Quick Depressurization makes its volume sharply
Expansion, obtains defluorination material, considerably increases the surface area of defluorination material, the fluorine adsorption site in defluorination material also increases therewith
It is more, to improve the fluorine adsorbance of defluorination material, improve defluorination effect.
In order to solve the above technical problems, technical solution provided by the invention is：A kind of preparation method of defluorination material, it is special
Sign is that this approach includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, then pulverize and sieve；
Step 2: acid solution is added in reed stem into step 1 after being sieved and stirs evenly to form mixed system,
Then mixed system is heated to reflux and carries out acidolysis for reed stem desugar；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried；
Step 4: acidolysis residue after drying in step 3 is carried out expanding treatment, defluorination material is obtained；It is described swollen
Changing the detailed process handled is：Acidolysis residue after drying is placed in the supplies room of pneumatic type extruding apparatus, object is worked as
When air pressure in material room reaches 0.1MPa~0.2MPa, fast-discharge valve Quick Depressurization is opened, so that acidolysis residue after drying
Volume sharply expands, and obtains defluorination material.Defluorination material is prepared using the extensive reed stem in source as raw material, passes through heating first
The sugar in reed stem is sloughed in acidolysis, and the surface of reed stem is made to form discontinuous massive texture, and hole occurs in inside, so
Reed stem after making desugar by expanding treatment afterwards is anxious but unable to do any thing acute expansion, and the specific surface area of defluorination material, fluorine removal material are considerably increased
Fluorine adsorption site in material also increases therewith, to improve the fluorine adsorbance of defluorination material, improves defluorination effect.
A kind of preparation method of above-mentioned defluorination material, which is characterized in that in acid solution described in step 2 containing hydrochloric acid and
Sulfuric acid, the concentration of the hydrochloric acid are 2mol/L~5mol/L, and the concentration of sulfuric acid is 1mol/L~3mol/L；It is described after being sieved
The ratio between quality and the volume of acid solution of reed stem are 1:(8~15), the unit of quality are g, and the unit of volume is mL；It is described to add
The temperature of heat reflux is 75 DEG C~95 DEG C, and the time is 2h~8h.By the optimization to heating acidolysis process parameter, reed is improved
The desugar efficiency of stem, simplifies preparation process, reduces the preparation cost of defluorination material.
In addition, the present invention also provides a kind of methods for removing fluorine ion in water removal using defluorination material, which is characterized in that should
Method includes the following steps：
It is uniformly mixing to obtain mixed liquor Step 1: defluorination material is added in fluoride waste, is then allowed to stand 30min；
It stirs evenly, is then allowed to stand Step 2: inorganic flocculating agent is added in step 1 in the mixed liquor after standing
30min；
It stirs evenly, is then allowed to stand Step 3: flocculation aid is added in step 2 in the mixed liquor after standing
30min.Defluorination material is directly added into fluoride waste and fluorine removal is carried out using flocculant and flocculation aid auxiliary, need to only mix and stir
The shirtsleeve operations such as standing are mixed and stirred, and operating process is controlled without accurate, it is convenient and easy, it is suitable for promoting the use of.
Above-mentioned method, which is characterized in that the additional amount of defluorination material described in step 1 is to add in every liter of fluoride waste
Enter 0.15g~0.9g defluorination material.It goes defluorination material additional amount needed for fluorine ion in water removal less using defluorination material, saves
The cost of material of fluorine removal.
Above-mentioned method, which is characterized in that inorganic flocculating agent described in step 2 is aluminium polychloride, polymeric aluminum sulfate iron
Or bodied ferric sulfate.Using aluminium salt polymer or molysite polymer as flocculant, it can effectively assist defluorination material removal fluorine-containing
Fluorinion in waste water enhances defluorination effect, and dosage is few, and flocculation ability is strong, easy to use, and residual activity aluminium in water
Or iron is less, will not influence human health or pollutes the environment, it is environmentally protective.
Above-mentioned method, which is characterized in that flocculation aid described in step 3 is polyacrylamide.The polypropylene of linear structure
Amide is acted on by adsorption bridging, is accelerated the formation of coagulum, and then accelerate settling velocity, is enhanced defluorination effect, from
And realize the purpose of auxiliary fluorine removal.
Above-mentioned method, which is characterized in that the mass ratio of the defluorination material, inorganic flocculating agent and flocculation aid is 10:3:
1.The defluorination material, inorganic flocculating agent and flocculation aid of the mass ratio are added into fluoride waste, makes to reach optimal between three
Synergistic action effect not only strengthens defluorination effect, but also avoids excessively making for defluorination material, inorganic flocculating agent and flocculation aid
With, be conducive to save fluorine removal raw material cost.
Compared with the prior art, the present invention has the following advantages：
1, reed stem desugar is made reed stem by heating acidolysis first using reed stem as raw material by the present invention
Surface and internal formation hole, then carry out expanding treatment, are pressurized using pressure-air to the reed stem after desugar, then quickly
Discharge expands its volume sharply, obtains defluorination material, considerably increases the specific surface area of defluorination material, the fluorine in defluorination material
Adsorption site also increases therewith, to improve the fluorine adsorbance of defluorination material, improves defluorination effect.
2, the raw material reed of the invention for preparing defluorination material is from a wealth of sources, cheap and easy to get, greatly reduces defluorination material
Cost of material, and the preparation process of defluorination material is brief, in the process without using expensive reagent, further reduced defluorination material
Preparation cost.
3, defluorination material is applied in the method for carrying out fluorine removal in fluoride waste by the present invention, only need to be mixed and stand
Equal shirtsleeve operations, and operating process is controlled without accurate, it is convenient and easy, it is suitable for promoting the use of.
4, the present invention removes fluorine ion in water removal using flocculant, flocculation aid auxiliary defluorination material, using flocculant and helps solidifying
The effects of adsorption bridging of agent, accelerates the formation of coagulum, and then accelerates settling velocity, enhances defluorination effect.
5, the flocculant poly aluminium chloride (PAC) of defluorination material of the present invention used in, polymeric aluminum sulfate iron
(PAFS) or bodied ferric sulfate (PFS) and flocculation aid polyacrylamide (PAM) are polymer, and residual activity aluminium in water is equal
It is less, it will not influence human health or pollute the environment, it is environmentally protective.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of pneumatic type extruding apparatus in 1~embodiment of the embodiment of the present invention 10.
Fig. 2 is the electron microscope for the reed stem that the embodiment of the present invention 1 is crossed after 40 meshes.
Fig. 3 is the electron microscope for the defluorination material that the embodiment of the present invention 1 is prepared.
Fig. 4 is the electron microscope for the defluorination material that comparative example 1 of the present invention is prepared.
Description of symbols
1-fast-discharge valve；2-material mouths；3-supplies rooms；
4-reversal valves；5-air gauges；6-actuated overflow valves；
7-air filters；8-air pumps；9-motors.
Specific embodiment
A kind of preparation method of defluorination material of the present invention is carried out specifically by 1~embodiment of embodiment 10 and comparative example 1
It is bright.
As shown in Figure 1, in 1~embodiment of the embodiment of the present invention 10 pneumatic type extruding apparatus include supplies room 3, reversal valve 4,
Air filter 7 and air pump 8, one end of the supplies room 3 offer material mouth 2, and the top of supplies room 3 is equipped with fast-discharge valve 1,
The supplies room 3 is successively connect with reversal valve 4, air filter 7 and air pump 8, between the reversal valve 4 and air filter 7
It is provided with actuated overflow valve 6, air gauge 5 is installed on the actuated overflow valve 6, the air pump 8 is connect with motor 9.
Embodiment 1
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 40 meshes；
Step 2: 160mL acid solution is added in the reed stem crossed after 40 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 75 DEG C and keeps the temperature reflux 2h to carry out acidolysis for reed stem desugar to mixed system；The acid solution
The concentration of middle hydrochloric acid is 2mol/L, and the concentration of sulfuric acid is 1mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.10MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Fig. 2 is the electron microscope that the present embodiment crosses the reed stem after 40 meshes, crosses the reed after 40 meshes as can be seen from Figure 2
The structure of reed stem is flat and smooth, and continuous tissue.
Fig. 3 is the electron microscope for the defluorination material that the present embodiment is prepared, as can be seen from Figure 3 the hole in defluorination material
More and big, specific surface area is larger, and adsorption site is also more.
After Fig. 2 and Fig. 3 to be compared to the structure that can be seen that the defluorination material that the present embodiment is prepared than crossing 40 meshes
The structure of reed stem is increasingly complex, and forms a large amount of hole, and specific surface area increases, but the overall structure of reed stem is complete
It is whole, it is not corrupted, illustrates the adsorbable more fluorine ions of defluorination material that embodiment is prepared, thus there is higher remove
Fluorine performance.
Comparative example 1
The preparation method of the defluorination material of this comparative example includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 40 meshes；
Step 2: 160mL acid solution is added in the reed stem crossed after 40 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 75 DEG C and keeps the temperature reflux 2h to carry out acidolysis for reed stem desugar to mixed system；The acid solution
The concentration of middle hydrochloric acid is 2mol/L, and the concentration of sulfuric acid is 1mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C, obtains fluorine removal material
Material.
Fig. 4 is the electron microscope for the defluorination material that this comparative example is prepared, from fig. 4, it can be seen that this comparative example is prepared into
The defluorination material arrived is cotton-shaped discontinuous structure, and occurs a little hole in tissue, and the specific surface area of defluorination material increases.
Fig. 3 and Fig. 4 are compared as can be seen that the defluorination material that embodiment 1 is prepared is removed than what comparative example 1 was prepared
The hole of fluorine material is more bigger, and specific surface area is bigger, and adsorption site is also more, illustrates that bulking processing art for producing effectively increases
Pore quantity and volume in defluorination material, to increase the specific surface area of defluorination material, the fluorine for increasing defluorination material is inhaled
Attached site improves the fluorine adsorbance of defluorination material, improves defluorination effect.
Embodiment 2
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 40 meshes；
Step 2: 160mL acid solution is added in the reed stem crossed after 40 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 75 DEG C and keeps the temperature reflux 3h to carry out acidolysis for reed stem desugar, obtains acidolysis to mixed system
Liquid；The concentration of hydrochloric acid is 2mol/L in the acid solution, and the concentration of sulfuric acid is 2.5mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.13MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Embodiment 3
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 50 meshes；
Step 2: 200mL acid solution is added in the reed stem crossed after 50 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 75 DEG C and keeps the temperature reflux 3h to carry out acidolysis for reed stem desugar, obtains acidolysis to mixed system
Liquid；The concentration of hydrochloric acid is 2.5mol/L in the acid solution, and the concentration of sulfuric acid is 1.5mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.15MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Embodiment 4
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 50 meshes；
Step 2: 200mL acid solution is added in the reed stem crossed after 50 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 80 DEG C and keeps the temperature reflux 4h to carry out acidolysis for reed stem desugar, obtains acidolysis to mixed system
Liquid；The concentration of hydrochloric acid is 2.5mol/L in the acid solution, and the concentration of sulfuric acid is 2mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.17MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Embodiment 5
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 50 meshes；
Step 2: 220mL acid solution is added in the reed stem crossed after 50 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 80 DEG C and keeps the temperature reflux 4h to carry out acidolysis for reed stem desugar, obtains acidolysis to mixed system
Liquid；The concentration of hydrochloric acid is 3mol/L in the acid solution, and the concentration of sulfuric acid is 2mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.18MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Embodiment 6
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 50 meshes；
Step 2: 220mL acid solution is added in the reed stem crossed after 50 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 85 DEG C and keeps the temperature reflux 5h to carry out acidolysis for reed stem desugar, obtains acidolysis to mixed system
Liquid；The concentration of hydrochloric acid is 3mol/L in the acid solution, and the concentration of sulfuric acid is 2.5mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.16MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Embodiment 7
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 60 meshes；
Step 2: 240mL acid solution is added in the reed stem crossed after 60 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 85 DEG C and keeps the temperature reflux 5h to carry out acidolysis for reed stem desugar, obtains acidolysis to mixed system
Liquid；The concentration of hydrochloric acid is 4mol/L in the acid solution, and the concentration of sulfuric acid is 2.5mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.15MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Embodiment 8
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 60 meshes；
Step 2: 240mL acid solution is added in the reed stem crossed after 60 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 80 DEG C and keeps the temperature reflux 6h to carry out acidolysis for reed stem desugar, obtains acidolysis to mixed system
Liquid；The concentration of hydrochloric acid is 4mol/L in the acid solution, and the concentration of sulfuric acid is 3mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.15MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Embodiment 9
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 60 meshes；
Step 2: 260mL acid solution is added in reed stem into 20g step 1 after 60 meshes and stirs evenly shape
At mixed system, then mixed system is heated to 90 DEG C and keeps the temperature reflux 7h to carry out acidolysis for reed stem desugar, obtains acid
Solve liquid；The concentration of hydrochloric acid is 4.5mol/L in the acid solution, and the concentration of sulfuric acid is 3mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.16MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
Embodiment 10
The preparation method of the defluorination material of the present embodiment includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, it then crushed 60 meshes；
Step 2: 300mL acid solution is added in the reed stem crossed after 60 meshes into 20g step 1 and stirs evenly to be formed
Then mixed system is heated to 95 DEG C and keeps the temperature reflux 8h to carry out acidolysis for reed stem desugar, obtains acidolysis to mixed system
Liquid；The concentration of hydrochloric acid is 5mol/L in the acid solution, and the concentration of sulfuric acid is 3mol/L；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is that acidolysis is residual
Excess then with deionized water flush acid solution residue to neutrality, then is dried under conditions of 80 DEG C；
Step 4: acidolysis residue after drying in step 3 is placed in pneumatic type extruding apparatus by material mouth 2
Supplies room 3 in, be then shut off material mouth 2, by motor 9 drive air pump 8, make air through air filter 7 filtering after lead to again
Reversal valve 4 is crossed to enter to the pressurization of acidolysis residue in supplies room 3, by observing the registration of air gauge 5 and adjusting actuated overflow valve 6
Folding, so that the air pressure in supplies room 3 is reached 0.20MPa, be then turned on 1 Quick Depressurization of fast-discharge valve, so that acidolysis after drying
Residual volume sharply expands, and obtains defluorination material.
The defluorination material that 1~embodiment of embodiment 10 and comparative example 1 are prepared carries out Fluoride-Absorption Capacity detection, specific mistake
Journey is as follows：0.5g defluorination material is added in 100mL fluoride waste (fluorinion concentration 5mg/L) and is stood after mixing evenly
30min using the content of fluoride ion in ion-selective electrode method solution, and calculates fluoride removing rate, fluoride removing rate (%)=(remove
Fluorinion concentration in fluoride waste after fluorinion concentration-fluorine removal in fluoride waste before fluorine) fluorine ion is dense in fluoride waste before/fluorine removal
Degree × 100%, as a result as shown in table 1 below.
The Fluoride-Absorption Capacity for the defluorination material that 1 1~embodiment of embodiment 10 of table and comparative example 1 are prepared
As shown in Table 1, the defluorination material that 1~embodiment of the embodiment of the present invention 10 and comparative example 1 are prepared is to fluorine-containing
Waste water has certain defluorination effect, wherein the Fluoride-Absorption Capacity for the defluorination material that embodiment 8 is prepared is best, to fluorine ion
Concentration is that the fluoride removing rate of the fluoride waste of 5mg/L is up to 72.80%, thereby determines that the preparation condition of defluorination material in embodiment 8
For defluorination material optimum condition of the present invention；Embodiment 1 and comparative example 1 are compared it is found that the defluorination material that embodiment 1 is prepared
Fluoride removing rate to be far longer than the fluoride removing rate of the defluorination material that comparative example 1 is prepared, illustrate that bulking processing art for producing increases and remove
The surface area of fluorine material increases fluorine adsorption site, to improve the fluorine adsorbance of defluorination material, improves defluorination effect.
The present invention is a kind of to go the method for fluorine ion in water removal to carry out by 11~embodiment of embodiment 30 using defluorination material
It is described in detail, defluorination material used in 11~embodiment of embodiment 30 is that embodiment 4 is prepared.
Embodiment 11
The method that the present embodiment application defluorination material removes fluorine ion in water removal includes the following steps：
It is uniformly mixing to obtain mixed liquor Step 1: 0.15g defluorination material is added in 1000mL fluoride waste, it is then quiet
Set 30min；Fluorinion concentration in the fluoride waste is 5mg/L；
It is stirred evenly Step 2: 0.05g aluminium polychloride is added in step 1 in the mixed liquor after standing, then
Stand 30min；
It is stirred evenly Step 3: 0.015g polyacrylamide is added in step 2 in the mixed liquor after standing, so
After stand 30min.
The effect of fluorine ion in water removal is gone to examine the present embodiment application defluorination material using fluorescence spectrophotometric method
Survey, and calculate fluoride removing rate, fluoride removing rate (%)=(before fluorine removal in fluoride waste after fluorinion concentration-fluorine removal in fluoride waste fluorine from
Sub- concentration) fluorinion concentration × 100% in fluoride waste before/fluorine removal.
12~embodiment of embodiment 30 is with embodiment 11 the difference is that additional amount, the inorganic flocculating agent of defluorination material
Type and additional amount, the type of flocculation aid and additional amount, details and using defluorination material go water removal in fluorine ion effect
As shown in table 2 below.
2 11~embodiment of embodiment 30 of table removes the technological parameter and defluorination effect of fluorine ion in water removal using defluorination material
"/" expression is added without this inorganic flocculating agent in table.
As known from Table 2, it is used alone and removes using defluorination material, inorganic flocculating agent and flocculation aid processing fluoride waste effect ratio
The defluorination effect of fluorine material is more preferable, and defluorination material, PAC, PAM combination defluorination effect to be substantially better than defluorination material,
The defluorination effect of PAFS, PAM combination or defluorination material, PFS, PAM combination, illustrates that PAC is formed on the hole surface of defluorination material
Al(OH)3Coagulation body film, effectively increases the adsorbance to fluorine ion, and the PAM polymer substance of linear structure passes through suction
Attached bridging action, accelerates the formation of coagulum, and then accelerates settling velocity, enhances defluorination effect；In addition, with fluoride removing rate
For index it can be concluded that the technological parameter of embodiment 23 is best, i.e., the additional amount of defluorination material is 0.45g/L, the additional amount of PAC
For 0.15g/L, when the additional amount of PAM is 0.045g/L, goes the efficiency of fluorine ion in water removal best using defluorination material, can reach
93.85%.
The above is only preferable profile embodiment of the invention, not does any restrictions to the present invention, all
According to inventive technique any simple modification substantially to the above embodiments, change and equivalent structural changes, this is still fallen within
In the protection scope of inventive technique scheme.
Claims (7)
1. a kind of preparation method of defluorination material, which is characterized in that this approach includes the following steps：
Step 1: reed stem is gone after soil to clean to air-dry, then pulverize and sieve；
Step 2: acid solution is added in reed stem into step 1 after being sieved and stirs evenly to form mixed system, then
Mixed system is heated to reflux and carries out acidolysis for reed stem desugar；
Step 3: the mixed system in step 2 after acidolysis is separated by solid-liquid separation, obtained solid content is acidolysis residue,
Then it with deionized water flush acid solution residue to neutrality, then is dried；
Step 4: acidolysis residue after drying in step 3 is carried out expanding treatment, defluorination material is obtained；At the extruding
The detailed process of reason is：Acidolysis residue after drying is placed in the supplies room of pneumatic type extruding apparatus, supplies room is worked as
In air pressure when reaching 0.1MPa~0.2MPa, fast-discharge valve Quick Depressurization is opened, so that acidolysis residual volume after drying
It sharply expands, obtains defluorination material.
2. a kind of preparation method of defluorination material according to claim 1, which is characterized in that in acid solution described in step 2
Containing hydrochloric acid and sulfuric acid, the concentration of the hydrochloric acid is 2mol/L~5mol/L, and the concentration of sulfuric acid is 1mol/L~3mol/L；It is described
The ratio between quality and the volume of acid solution of reed stem after being sieved are 1:(8~15), the unit of quality are g, the unit of volume
For mL；The temperature being heated to reflux is 75 DEG C~95 DEG C, and the time is 2h~8h.
3. a kind of method that the defluorination material using the preparation of preparation method described in claims 1 or 2 removes fluorine ion in water removal,
It is characterized in that, this approach includes the following steps：
It is uniformly mixing to obtain mixed liquor Step 1: defluorination material is added in fluoride waste, is then allowed to stand 30min；
It stirs evenly, is then allowed to stand Step 2: inorganic flocculating agent is added in step 1 in the mixed liquor after standing
30min；
It is stirred evenly Step 3: flocculation aid is added in step 2 in the mixed liquor after standing, is then allowed to stand 30min.
4. according to the method described in claim 3, it is characterized in that, the additional amount of defluorination material described in step 1 contains for every liter
0.15g~0.9g defluorination material is added in fluorine waste water.
5. according to the method described in claim 3, it is characterized in that, inorganic flocculating agent described in step 2 be aluminium polychloride,
Polymeric aluminum sulfate iron or bodied ferric sulfate.
6. according to the method described in claim 3, it is characterized in that, flocculation aid described in step 3 is polyacrylamide.
7. according to the method described in claim 3, it is characterized in that, the matter of the defluorination material, inorganic flocculating agent and flocculation aid
Amount is than being 10:3:1.
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Application publication date: 20181130 |