CN110038510B - Preparation method of modified calcite adsorbent for fluorine removal - Google Patents
Preparation method of modified calcite adsorbent for fluorine removal Download PDFInfo
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- CN110038510B CN110038510B CN201910352111.1A CN201910352111A CN110038510B CN 110038510 B CN110038510 B CN 110038510B CN 201910352111 A CN201910352111 A CN 201910352111A CN 110038510 B CN110038510 B CN 110038510B
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- 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
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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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- 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
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- 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
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- C02F2101/14—Fluorine or fluorine-containing compounds
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Abstract
The invention relates to a preparation method of a modified calcite adsorbent for defluorination, which comprises the steps of firstly preparing a mixed solution of disodium hydrogen phosphate and sodium chloride, adding calcite powder into the mixed solution, wherein the solid-liquid ratio is 15-25g/L, uniformly mixing, adjusting the pH value of 8, stirring at room temperature for reaction, adjusting and keeping the pH value of a reaction system to be 8 during the stirring reaction, obtaining a reaction liquid after the reaction is finished, carrying out suction filtration, washing a filter cake with deionized water, freeze-drying the filter cake, grinding to obtain modified material powder, uniformly mixing the modified material powder with attapulgite powder according to the volume ratio of 8-15:1 to obtain material powder, adding the material powder into a sugar coating machine, dropwise adding deionized water for granulation to obtain spherical particles, calcining the spherical particles in a muffle furnace, and cooling to obtain the modified calcite adsorbent. The method is simple and low in cost, and the prepared modified calcite adsorbent has excellent adsorption performance on fluorine ions in an aqueous solution.
Description
Technical Field
The invention relates to a preparation method of a modified calcite adsorbent for fluorine removal, belonging to the technical field of environmental remediation.
Background
Fluorine is a non-metallic element widely distributed in nature, and two main fluorine sources exist in nature, one is fluorine element contained in industrial waste discharged to the environment by human industrial activities; and the other is that various naturally formed and widely distributed fluorine-containing minerals enter the atmosphere, soil and underground water after weathering and transportation. The second source is the most important, and under the condition of proper geological environment, the naturally released fluorine is collected to form a natural enrichment area, which causes serious fluorine pollution of soil, underground water and the like. People drink high-fluorine water in polluted areas for a long time to damage tooth bones and even cause disabilities; damage to liver, brain, etc. and influence on immune function; the thyroid gland is destroyed, and death results in severe cases.
The disease of chronic fluorosis in the whole body caused by excessive fluorine content in the environment is called endemic fluorosis, abbreviated as difluoride disease, and is clinically mainly manifested as dental fluorosis and fluorosis disease. The disease is a worldwide endemic disease, reported by 'UNICEF India', the disease is widely distributed in more than 25 countries and regions in Asia, Europe, Africa and America, and China is also a high-incidence region of the disease. The difluropathy is one of four endemic diseases (the difluropathy, the keshan disease, the Kaschin-Beck disease and the endemic goiter) prevalent in China, areas affected by the difluropathy exist in all provinces except Shanghai, 1226 disease areas are located in counties of China, more than two hundred million people are affected by threatened population, and the most main drinking water type fluorine pollution is distributed throughout the country. Therefore, the treatment of fluorine pollution, especially the treatment of fluorine pollution of drinking water, is not slow.
Common main methods for removing fluorine ions in water to treat fluorine pollution of drinking water comprise a precipitation flocculation method, an ion exchange method, an electrochemical method, a membrane filtration method, an adsorption method and the like. The precipitation flocculation method has obvious effect, but the excessive use of the medicament can cause pH unbalance and secondary pollution; the ion exchange method has low treatment efficiency on a large amount of sewage, and the ion exchange resin has high price and high cost; the electrochemical method has huge energy consumption and is not paid; the semipermeable membrane used in the membrane filtration method is high in price, and the regeneration and maintenance technology is complex and difficult to popularize. Compared with the traditional defluorination methods, the adsorption method has the advantages of low cost, obvious effect and environmental protection, and is an ideal technical means.
The adsorption method adopts the basic principle of interfacial adsorption, namely, the aim of reducing the concentration of target ions in the solution is achieved through the actions of ion exchange reaction, lattice coprecipitation, surface precipitation and the like which occur on an aqueous solution-mineral interface. The key of the adsorption method fluorine removal technology lies in finding a proper adsorbent, the commonly used fluorine adsorbents comprise activated alumina, ferric hydroxide, montmorillonite, calcite, hydroxyapatite and the like, and the activated alumina has the strongest fluorine removal capability but high price; the hydroxyapatite has stronger defluorination capability but has the defects of poor permeability, natural passivation, low material utilization rate and the like; and the other adsorbents have weak fluorine removal capacity, need to be applied in large quantity and cause inconvenience in use.
Calcite is one of the most abundant and widely distributed minerals in nature, is applied to various sedimentary rocks such as limestone and biological shells, has the lowest price, is most easily obtained, has the largest resource amount, is an ideal mineral chemical raw material, also has certain fluorine removal capability, but has poor fluorine removal performance due to the influence of the components and the structure of the calcite. The apatite minerals in nature also have the isomorphism replacement process of carbonate and the like with phosphate radicals in the structure, which shows that the composition structure of calcite is possible to be converted into apatite, and the successful phosphorylation modification of calcite can greatly improve the fluoride removal capability of calcite by combining the strong fluoride removal capability of apatite.
At present, the application of calcite in the field of fluorine removal still remains on the traditional means of directly applying raw ore powder and high-fluorine water for mixed adsorption, for example, methods such as structure and component modification in the research field of other mineral materials are not widely tried, and the method of directly applying the calcite by grinding powder does not substantially improve the properties of calcite, such as material composition, surface structure property and the like, which influence the fluorine removal capability, so that the application of the calcite in the field of fluorine removal is greatly influenced, and the technical bottleneck is formed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art that calcite is adopted as a fluorine adsorbent, and provides a preparation method of a modified calcite adsorbent for removing fluorine, which is simple and has excellent adsorption performance on fluorine ions in an aqueous solution.
Technical scheme
The preparation method of the modified calcite adsorbent for removing fluorine comprises the following steps:
(1) preparing a mixed solution of disodium hydrogen phosphate and sodium chloride, adding calcite powder into the mixed solution, wherein the solid-to-liquid ratio is 15-25g/L, uniformly mixing, adjusting the pH value of 8, stirring at room temperature for reaction, adjusting and keeping the pH value of a reaction system to be 8 in the stirring reaction process, and obtaining a reaction solution after the reaction is finished;
(2) carrying out suction filtration on the reaction liquid, then washing a filter cake with deionized water, carrying out freeze drying on the filter cake, and then grinding to obtain modified material powder;
(3) uniformly mixing the modified material powder and the attapulgite powder in a volume ratio of 8-15:1 to obtain material powder, adding the material powder into a sugar-coating machine, dropwise adding deionized water for granulation to obtain spherical particles, calcining the spherical particles in a muffle furnace, and cooling to obtain the modified calcite adsorbent for removing fluorine.
Further, in the step (1), the mixed solution of disodium hydrogenphosphate and sodium chloride has a mass concentration of 0.12% and a mass concentration of 0.06% respectively.
Further, in the step (1), the solid-to-liquid ratio of the calcite powder to the mixed solution is 20 g/L.
Further, in the step (3), the volume ratio of the modified material powder to the attapulgite powder is 10: 1.
Further, in the step (3), the diameter of the spherical particles is 2-4 mm.
Further, in the step (3), the calcination temperature is 700-.
The invention has the beneficial effects that:
1) according to the invention, the surface of calcite is subjected to phosphorylation modification, the specific surface area of calcite powder is increased, the surface of the calcite is provided with a phosphated layer with strong defluorination capability such as hydroxyapatite, carbon apatite and the like, and the defluorination performance of the calcite is greatly improved through modification, so that the method is beneficial to wider application in the field of water body fluorine pollution treatment and has a very wide application prospect.
2) According to the invention, calcite is used as a raw material to prepare the adsorbent, the advantages of easiness in obtaining calcite, low cost, wide source, large resource amount and the like are effectively utilized, meanwhile, industrial-grade sodium dihydrogen phosphate is very low in price, and the combination of the calcite and the industrial-grade sodium dihydrogen phosphate greatly reduces the fluorine removal cost, has high cost performance, has strong competitiveness compared with other common fluorine adsorbents, and endows the calcite with greater economic and environmental benefits.
3) The modified material and the attapulgite powder are mixed, granulated and subjected to heat treatment to prepare the water-resistant particles, which shows that the material has strong practicability and has huge potentials of industrialization and commercialization.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The preparation method of the modified calcite adsorbent for removing fluorine comprises the following steps:
(1) preparing a mixed solution of disodium hydrogen phosphate and sodium chloride, wherein the mass concentration of the disodium hydrogen phosphate is 0.12% and the mass concentration of the sodium chloride is 0.06%, adding calcite powder into the mixed solution, the solid-to-liquid ratio is 20g/L, uniformly mixing, adjusting the pH value to 8, stirring and reacting at room temperature, adjusting and keeping the pH value of a reaction system to be 8 in the stirring and reacting process, and obtaining a reaction solution after the reaction is finished;
(2) filtering the reaction solution, washing the filter cake with deionized water, freeze-drying the filter cake, and grinding to obtain modified material powder (the specific surface area of the modified material powder is 17.91 m)2Per g, and the specific surface area of the calcite powder is 0.74m2/g)；
(3) Uniformly mixing the modified material powder and the attapulgite powder in a volume ratio of 10:1 to obtain material powder, adding the material powder into a sugar-coating machine, dropwise adding deionized water for granulation to obtain spherical particles with the diameter of 3mm, calcining the spherical particles in a muffle furnace (the calcining temperature is 750 ℃ and the calcining time is 4 hours), and then cooling to obtain the modified calcite adsorbent for removing fluorine.
Example 2
The preparation method of the modified calcite adsorbent for removing fluorine comprises the following steps:
(1) preparing a mixed solution of disodium hydrogen phosphate and sodium chloride, wherein the mass concentration of the disodium hydrogen phosphate is 0.12% and the mass concentration of the sodium chloride is 0.06%, adding calcite powder into the mixed solution, the solid-to-liquid ratio is 20g/L, uniformly mixing, adjusting the pH value to 8, stirring and reacting at room temperature, adjusting and keeping the pH value of a reaction system to be 8 in the stirring and reacting process, and obtaining a reaction solution after the reaction is finished;
(2) carrying out suction filtration on the reaction liquid, then washing a filter cake with deionized water, carrying out freeze drying on the filter cake, and then grinding to obtain modified material powder;
(3) uniformly mixing the modified material powder and the attapulgite powder in a volume ratio of 8:1 to obtain material powder, adding the material powder into a sugar-coating machine, dropwise adding deionized water for granulation to obtain spherical particles with the diameter of 4mm, calcining the spherical particles in a muffle furnace (the calcining temperature is 750 ℃ and the calcining time is 4 hours), and then cooling to obtain the modified calcite adsorbent for removing fluorine.
And (3) testing the defluorination effect:
preparing 0.5mM NaF and 0.01M NaCl mixed solution as simulated fluorine-containing wastewater, respectively taking 500mL of the wastewater in 3 big beakers, respectively adding the modified calcite adsorbent for removing fluorine and 1.25g of calcite raw material powder in the examples 1-2 into the three beakers, uniformly mixing, then adjusting the pH to 6, stirring and reacting at room temperature for 48 hours, adjusting the pH to keep stable at 6, filtering after the reaction is finished, measuring the fluorine ion concentration in the residual solution (namely during balance) by a fluorine ion selective electrode method, and calculating the fluorine removal rate according to the initial fluorine ion concentration and the ion concentration during balance.
The fluorine removal rate of the modified calcite adsorbent in example 1 was 71.71%, the fluorine removal rate of the modified calcite adsorbent in example 2 was 68.26%, and the fluorine removal rate of the calcite raw material powder was 3.53%.
Claims (5)
1. The preparation method of the modified calcite adsorbent for fluorine removal is characterized by comprising the following steps:
(1) preparing a mixed solution of disodium hydrogen phosphate and sodium chloride, adding calcite powder into the mixed solution, wherein the solid-to-liquid ratio is 15-25g/L, uniformly mixing, adjusting the pH to 8, stirring at room temperature for reaction, adjusting and maintaining the pH of a reaction system to be 8 in the stirring reaction process, and obtaining a reaction solution after the reaction is finished;
(2) carrying out suction filtration on the reaction liquid, then washing a filter cake with deionized water, carrying out freeze drying on the filter cake, and then grinding to obtain modified material powder;
(3) uniformly mixing the modified material powder and the attapulgite powder in a volume ratio of 8-15:1 to obtain material powder, adding the material powder into a sugar-coating machine, dropwise adding deionized water for granulation to obtain spherical particles, calcining the spherical particles in a muffle furnace, and cooling to obtain the modified calcite adsorbent for removing fluorine;
in the step (3), the calcination temperature is 700-800 ℃, and the time is 3-6 h.
2. The method for producing a modified calcite adsorbent for fluorine removal according to claim 1, wherein in step (1), the mixed solution of disodium hydrogenphosphate and sodium chloride has a disodium hydrogenphosphate concentration of 0.12% by mass and a sodium chloride concentration of 0.06% by mass.
3. The method for preparing the modified calcite adsorbent for fluorine removal according to claim 1, wherein in step (1), the solid-to-liquid ratio of the calcite powder to the mixed solution is 20 g/L.
4. The method for preparing the modified calcite adsorbent for fluorine removal according to claim 1, wherein in step (3), the volume ratio of the modified material powder to the attapulgite powder is 10: 1.
5. The process for preparing modified calcite adsorbent for fluorine removal according to claim 1 wherein in step (3) the spherical particles have a diameter of 2-4 mm.
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| CN103058344A (en) * | 2009-11-13 | 2013-04-24 | 江苏永冠给排水设备有限公司 | Novel defluoridation filter material and production method thereof |
| CN102502907B (en) * | 2011-10-14 | 2013-06-26 | 江苏永冠给排水设备有限公司 | Production method of attapulgite loaded hydroxyapatite composite defluorination filter bulb |
| CN102380350B (en) * | 2011-10-24 | 2013-06-05 | 上海海洋大学 | Method for removing hydroxyapatite modified eggshell adsorbent material and recycling phosphate from wastewater |
| CN108479693A (en) * | 2018-05-04 | 2018-09-04 | 成都理工大学 | Hydroxyapatite attapulgite composite material and its preparation method and application |
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