CN112429825A - Defluorination agent and preparation method thereof - Google Patents
Defluorination agent and preparation method thereof Download PDFInfo
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- CN112429825A CN112429825A CN202011189451.6A CN202011189451A CN112429825A CN 112429825 A CN112429825 A CN 112429825A CN 202011189451 A CN202011189451 A CN 202011189451A CN 112429825 A CN112429825 A CN 112429825A
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/10—Inorganic compounds
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Abstract
The invention discloses a preparation method of a fluorine removal agent, which comprises the following steps: (1) mixing thermoplastic starch with deionized water, stirring overnight in a magnetic stirrer to obtain a uniform solution, adding phosphorylase into the solution, carrying out catalytic reaction for 30-60 min at normal temperature, then adding liquid paraffin, stirring until the solution is uniform, adding a pore-forming agent, and heating in a water bath at 60-80 ℃ for 1-3 h to obtain a product a; preparing rare earth salt into a rare earth salt solution with a certain concentration; (2) mixing the obtained product a with a rare earth ion solution, adding a cross-linking agent, placing the mixture on a magnetic stirrer to fully react for 10-16 h, filtering the mixture by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying the cleaned filter cake, grinding the powder, sieving the powder by using a 100-mesh sieve to obtain a fluorine removal agent, and finally placing the fluorine removal agent into a dryer to be stored for later use. The defluorinating agent obtained by the method has the characteristics of high defluorinating speed, high defluorinating efficiency, low cost and no pollution.
Description
Technical Field
The invention belongs to the technical field of fluorine removal materials, and particularly relates to a fluorine removal agent and a preparation method thereof.
Background
Fluorine is one of the elements which are distributed on the earth surface most widely, the content of each element which forms the earth crust is sixteenth, and the fluorine accounts for 0.077 percent of the total amount of the earth crust and is an inherent chemical substance in nature; in the second period and the VIIA group of the periodic Table of the elements, the symbol of the element is F, the atomic number is 9, the atomic weight is 19.0, and the electronic configuration is 2S22P5The electronegativity is as high as 4.0, the first position of all elements is occupied, the geochemical electrovalence is-1, the covalent radius is 64pm, the ionic potential is-0.75, and the Ek value is 0.37 (-1). Therefore, fluorine is a non-metallic element with extremely strong electronegativity, has strong electron affinity, has the strongest non-metal property among all non-metallic elements, is active in chemical property, and is easy to exist in a compound state, so that fluorine does not exist in nature and exists mostly in an inorganic compound state.
Proper amount of fluorine has certain effect of preventing and treating decayed tooth and is an essential component for maintaining normal development of bones in vivo. However, excessive fluorine intake affects absorption of calcium and phosphorus in human body, and causes fluorosis symptoms such as fluorosis and fluoroplaque. Excessive fluorine intake also has adverse effects on nervous system, endocrine system and cotton-padded clothes, and can cause diseases such as brain injury and senile dementia. The high-fluorine underground water in China is widely distributed and spread over 27 provincial and urban autonomous regions, and is most serious in North China and northwest China. The world health organization recommends that the concentration of fluoride in drinking water is not more than 1.5mg/L, and the current drinking water standard in China stipulates that the concentration of fluoride is not more than 1.0 mg/L. Until now, a great deal of scientific research work has been carried out on how to treat fluorine-containing drinking water at home and abroad.
The commonly used method for removing the fluorine ions in the fluorine-containing drinking water comprises the following steps: adsorption, ion exchange, precipitation, membrane filtration, electroflocculation, electrodialysis, and the like.
The adsorption method is simple and convenient to operate and most widely applied. The most commonly used defluorinating agents are activated alumina and activated carbon. The adsorption method has the advantages that the removal rate of fluoride ions in the fluorine-containing drinking water can reach more than 90 percent, the source is wide, the cost is low, and therefore, the application range is wide, but the following defects exist: firstly, the adsorption process is highly dependent on the acidity of the environment, and the pH range is usually required to be 5.0-6.0; ② there is competition relation between the introduced sulfate, phosphate or carbonate and fluorinion, which is not good for adsorption; thirdly, the adsorption capacity is low, the mechanical strength is low and pretreatment is needed; fourthly, regeneration is needed after the catalyst is used for 4 to 5 months, and each regeneration can influence the adsorption capacity; cleaning the fluorine-containing sludge and the regenerant with the same problems.
The ion exchange method is to exchange anion exchange resin containing quaternary amino group with fluorinion until all the replaceable sites on the resin are replaced, then to clean the resin in a water reflux mode, and to replace fluorinion with new chlorion to realize the recycling of the resin, wherein the power of replacing chlorion with fluorinion is provided by the electronegativity of fluorinion. The adsorption percentage of the ion exchange method can reach 90-95%, and the color and taste of raw water can be retained to the maximum extent. The main disadvantages include: firstly, when sulfate radicals, carbonate radicals, phosphate radicals or alkaline substances exist in the water body, the adsorption percentage can be reduced; secondly, wastes rich in fluoride are generated during recycling, and treatment is needed before final treatment; the cost of the used resin is high, the pretreatment needs to maintain certain acidity, and the cost is increased by regenerating and treating wastes; fourthly, the pH value of the treated water body is lower and the content of chloride ions is higher.
The most common precipitation method is to add calcium salt, aluminum salt, iron salt and the like as a precipitator or a coagulant, and the method is simple to operate and low in cost, but generates a large amount of sludge in the precipitation process to bring secondary pollution. The electrochemical method does not need to add chemical agents, the defluorination equipment is simple, automatic control can be realized, but the power consumption is high, and the aluminum oxide compound generated by electrode electrolysis is easy to form a film on the surface of the anode, so that the electrode is passivated. The defluorination by the membrane separation technology has higher requirements on the quality of raw water, and if the quality of the raw water is poor, the membrane is polluted and blocked, so that the service life is influenced, and in addition, the membrane price and the equipment cost are higher. Ion exchange methods have poor selectivity for fluoride ions in solution.
Among many fluorine removal technologies, the adsorption method is widely adopted due to the advantages of simple operation, stable effect, economy, feasibility and the like, the fluorine removal efficiency of the adsorption method mainly depends on the performance of the adsorption material, the adsorption material is generally a porous substance with a dense pore structure and a large specific surface area, and the surface of the adsorption material is provided with groups suitable for forming chemical bonds under the action of fluorine ions. The activated alumina is the earliest defluorinating agent in China, but has the disadvantages of low defluorinating efficiency, few regeneration times and the like.
The position of the rare earth elements in the periodic table is different from that of common metal elements, and the rare earth elements have special electron shell structures, such as La to Lu (lanthanide series), and the electron shell structures are respectively as follows: 1S2, 2S2, 2P6, 3S2, 3P6, 3d10, 4S2, 4P6, 4d10, 5S2, 5P6 are all full, and the rest are 4f0-14, 5d1, 6S2, that is: electrons on the 4f.5d.6S orbital are easily lost to form cations. Taking La and Ce as examples, when 2 electrons on the 6S orbital are lost, the valence is + 2; however, one electron on the 4f orbital is also easily lost, and when lost, becomes 4f05d06S0 empty and in a steady state, the valence is + 3. Taking Gd and Tb as examples, their valence electron layer structures are 4f 75 d 16S 2, 4f 96S 2, respectively, and when two electrons on the 6S orbital are lost, the valence is +2, when one electron on the 5d orbital and 2 electrons on the 4f orbital are lost, the valence is Gd +3, Tb +4, and at this time the 4f orbital is in a stable state of half-full (4f 7). The latter Yb and Lu are similar to the above, but the 4f orbital is in a fully filled (4f14) steady state, with the middle electrons in the 4f orbital, such as Dy, Er, Tm, being between half-filled and fully empty. Rare earth chlorides, carbonates, nitrates, fluorides and other halides and rare earth oxides have an oxidation state of substantially +3 due to similar electronic arrangement (configuration) of the outer layers. However, the number of electrons in the inner layer 4f also has a certain influence on the valence state, Ce,Pr and Tb can be oxidized into +4 to form corresponding stable oxide CeO2、Pr6O11、Tb4O7Sm, Eu and Yb can be reduced to +2 to form abnormal valence compounds such as SmS.
Rare earth is an element with extremely strong chemical activity and has extremely strong affinity to hydrogen, carbon, nitrogen, oxygen, sulfur, phosphorus and halogen. Lanthanides are fairly strong active metals and the reactivity is related to lanthanide shrinkage. "lanthanide shrinkage" is an important phenomenon in inorganic chemistry, as a result of which Y is a shrinkage of the lanthanide3+The ionic radius will fall into Er3+Yttrium is hereinafter referred to as a member of the rare earth elements and is naturally associated with lanthanides. Rare earths can be generally classified into: light rare earth or cerium group rare earth (La, Ce, Pr, Nd, Pm, Sm, Eu); heavy rare earth or yttrium group rare earth (Gd, Tb, Py, Ho, R, Tm, Yb, Lu, Y). The light rare earth is easily oxidized in air at room temperature, and the heavy rare earth, Sc and Y form an oxidation protective layer at room temperature, so the rare earth is generally stored in kerosene or placed in a vacuum and argon-filled sealed container.
The rare earth elements are typical metal elements, the metal activity of which is inferior to that of alkali metals and alkaline earth metals, and of the 17 kinds of rare earth elements, the metal activity is increased from scandium, yttrium and lanthanum, but is decreased from lanthanum to lutetium, so that lanthanum is most active among the rare earth elements.
Among many defluorinating agents, rare earth has received wide attention due to its advantages of fast adsorption speed, large adsorption capacity, etc., among which, the mechanism of defluorination of hydrated rare earth oxide is the hydroxyl and F on the surface of oxide-Ion exchange occurs between them. The rare-earth ions being of the class of hard acids, optionally with F being of the class of hard bases-Has stronger coordination ability and the obtained complex is more stable. In addition, the safety limit standard of the rare earth oxide is 2.0mg/kg in the limit of pollutants in food (GB2762-2005), which indicates that the rare earth oxide with low dosage has certain safety. However, the direct treatment of fluorine-containing drinking water by using rare earth ions has the defects of high cost, difficult subsequent treatment, difficult reutilization and the like. In recent years, a great deal of research has been focused on loading rare earth ions to a low-cost, mechanically strong and green materialThe method has the advantages that the method is good in compatibility and environment-friendly, so that the cost of using rare earth is reduced, the subsequent operation is convenient, and the renewable utilization can be realized.
Thermoplastic starch generally refers to a disordered continuous phase of starch molecular chains, which is finally formed by applying heat energy and mechanical energy to raw starch in the presence of water or other plasticizers to break hydrogen bonds between starch molecules, so that crystalline structures in raw starch particles are disintegrated through melting and shearing actions. The starch material obtained here behaves as a thermoplastic and can be further processed into various articles using conventional plastic processing equipment.
At present, the adsorption research of rare earth modified chitosan resin on fluorinion is available, but the defluorination effect of the defluorination material obtained by rare earth modified chitosan resin is not ideal. The inventor prepares the fluorine removal agent by modifying the thermoplastic starch through the rare earth element based on the properties of the rare earth element and the thermoplastic starch, and the result proves that the fluorine removal agent has good fluorine removal effect and can be recycled.
Disclosure of Invention
The invention mainly aims to solve the problem that the existing defluorinating material has poor effect, and provides a defluorinating agent and a preparation method thereof. The fluorine removing agent has good fluorine removing effect and can be recycled for multiple times.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.
The invention provides a preparation method of a fluorine removal agent, which comprises the following steps:
(1) mixing thermoplastic starch with deionized water, stirring overnight in a magnetic stirrer to obtain a uniform solution, adding phosphorylase into the solution, carrying out catalytic reaction for 30-60 min at normal temperature, then adding liquid paraffin, stirring until the solution is uniform, adding a pore-forming agent, and heating in a water bath at 60-80 ℃ for 1-3 h to obtain a product a;
preparing rare earth salt into a rare earth salt solution with a certain concentration;
(2) mixing the obtained product a with a rare earth ion solution, adding a cross-linking agent, placing the mixture on a magnetic stirrer to fully react for 10-16 h, filtering the mixture by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying the cleaned filter cake, grinding the powder, sieving the powder by using a 100-mesh sieve to obtain a fluorine removal agent, and finally placing the fluorine removal agent into a dryer to be stored for later use.
The preparation method of the foregoing, wherein the thermoplastic starch has a density: 1.2g/cm3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3％。
In the preparation method, the thermoplastic starch and the deionized water are mixed according to the ratio of 1g of thermoplastic starch to 2-5 ml of deionized water.
In the preparation method, the mass ratio of the phosphorylase to the thermoplastic starch is 1: (50-100) is added.
In the preparation method, the pore-forming agent is selected from any one of dibutyl phthalate, polyethylene glycol or ethyl acetate.
The production method described above, wherein the rare earth salt is selected from a nitrate of any one of the following groups: la, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
In the preparation method, the concentration of the rare earth ion solution is 1-2 wt%.
In the preparation method, the product a and the rare earth ion solution are mixed according to the volume ratio of (1-10): 1.
In the preparation method, the crosslinking agent is epichlorohydrin or glutaraldehyde.
The purpose of the invention and the technical problem to be solved are also realized by adopting the following technical scheme.
The invention provides a fluorine removal agent, which is prepared according to the method.
By the technical scheme, the invention at least has the following advantages: according to the invention, thermoplastic starch is taken as a base material, phosphate groups are grafted to the thermoplastic starch under the action of phosphorylase, active groups in the thermoplastic starch can be exposed under the activation action of liquid paraffin, then a pore-forming agent is added to enable the thermoplastic starch to be in a porous form, finally, under the action of a cross-linking agent, rare earth ions are loaded in the pores of the thermoplastic starch, and the obtained fluorine removal agent has a plurality of sites combined with fluorine ions and can be effectively combined with the fluorine ions in sewage to remove the fluorine ions in the water. According to the invention, the thermoplastic starch is used as a carrier, and the rare earth ions are loaded on the treated thermoplastic starch through the crosslinking action of the crosslinking agent, so that the fluorine removal effect of the prepared fluorine removal agent is effectively improved. The defluorinating agent has the characteristics of high defluorinating speed, high defluorinating efficiency, low cost and no pollution, and the performance of the defluorinating agent is easy to recover, the preparation process is simple, and the production period is short. Therefore, the invention has extremely high application value.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
100g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) of the mixed solution and 300mL of deionized water are mixed and stirred in a magnetic stirrer overnight to obtain a uniform solution, 1g of phosphorylase is added into the solution to perform catalytic reaction for 50min at normal temperature, then liquid paraffin is added to perform stirring until the solution is uniform, 5g of dibutyl phthalate is added, and the mixture is heated in water bath at 70 ℃ for 2h to obtain a product a; lanthanum nitrate was formulated to a concentration of 1.5wt% lanthanum nitrate solution. Mixing 300mL of the obtained product a with 100mL of lanthanum nitrate solution, adding 5g of epoxy chloropropane, placing on a magnetic stirrer for full reaction for 13h, filtering by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying after cleaning, grinding into powder, sieving by using a 100-mesh sieve to obtain a defluorinating agent, and finally placing in a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 0.15mg/L, and the removal rate is 99.99%.
Example 2
100g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) of the mixed solution and 500mL of deionized water are mixed and stirred in a magnetic stirrer overnight to obtain a uniform solution, 2g of phosphorylase is added into the solution to perform catalytic reaction for 60min at normal temperature, then liquid paraffin is added to perform stirring until the solution is uniform, 10g of ethyl acetate is added, and the mixture is heated in a water bath at 60 ℃ for 3h to obtain a product a; neodymium nitrate was prepared as a 2 wt% neodymium nitrate solution. Mixing 500mL of the obtained product a with 100mL of neodymium nitrate solution, then adding 8g of epoxy chloropropane, placing the mixture on a magnetic stirrer for full reaction for 10h, filtering the mixture by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying the cleaned mixture, grinding the mixture into powder, sieving the powder by using a 100-mesh sieve to obtain a defluorinating agent, and finally placing the defluorinating agent into a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 0.23mg/L, and the removal rate is 99.98%.
Example 3
100g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) was mixed with 200mL of deionized water and stirred overnight in a magnetic stirrer to give a homogeneous solution, to which 0 was added.5g of phosphorylase undergoes catalytic reaction for 30min at normal temperature, then liquid paraffin is added to be stirred until the solution is uniform, 8g of dibutyl phthalate is added, and the mixture is heated in water bath for 2h at 80 ℃ to obtain a product a; preparing the cerium nitrate into a cerium nitrate solution with the concentration of 1 wt%. Mixing 200mL of the obtained product a with 20mL of cerium nitrate solution, then adding 2g of epoxy chloropropane, placing the mixture on a magnetic stirrer for full reaction for 16h, filtering the mixture by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying the cleaned filter cake, grinding the powder, sieving the powder by using a 100-mesh sieve to obtain a defluorinating agent, and finally placing the defluorinating agent into a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 0.19mg/L, and the removal rate is 99.98%.
Example 4
100g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) of the mixed solution and 400mL of deionized water are mixed and stirred in a magnetic stirrer overnight to obtain a uniform solution, 2g of phosphorylase is added into the solution to perform catalytic reaction for 40min at normal temperature, then liquid paraffin is added to perform stirring until the solution is uniform, 10g of ethyl acetate is added, and the mixture is heated in water bath at 70 ℃ for 1h to obtain a product a; lanthanum nitrate was formulated to a concentration of 1 wt%. Mixing 400mL of the obtained product a with 400mL of lanthanum nitrate solution, then adding 10g of glutaraldehyde, placing on a magnetic stirrer for full reaction for 10h, filtering by qualitative filter paper after the reaction is finished, cleaning a filter cake by ultrapure water, drying after cleaning, grinding into powder, sieving by a 100-mesh sieve to obtain a defluorinating agent, and finally placing in a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 0.18mg/L, and the removal rate is 99.99%.
Example 5
80g of thermoplastic starch (density: 1.2) are takeng/cm3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) of the mixed solution and 400mL of deionized water are mixed and stirred in a magnetic stirrer overnight to obtain a uniform solution, 2g of phosphorylase is added into the solution to perform catalytic reaction for 30min at normal temperature, then liquid paraffin is added to perform stirring until the solution is uniform, 2g of ethyl acetate is added, and the mixture is heated in water bath at 80 ℃ for 1h to obtain a product a; praseodymium nitrate is prepared into a praseodymium nitrate solution with the concentration of 2 wt%. Mixing 400mL of the obtained product a with 200mL of praseodymium nitrate solution, then adding 5g of glutaraldehyde, placing on a magnetic stirrer for full reaction for 12h, filtering by qualitative filter paper after the reaction is finished, cleaning a filter cake by ultrapure water, drying after cleaning, grinding into powder, sieving by a 100-mesh sieve to obtain a defluorinating agent, and finally placing in a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 0.2mg/L, and the removal rate is 99.98%.
Example 6
50g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) of the mixed solution and 200mL of deionized water, stirring the mixed solution in a magnetic stirrer overnight to obtain a uniform solution, adding 1g of phosphorylase into the solution to perform catalytic reaction for 30min at normal temperature, then adding liquid paraffin to stir the solution until the solution is uniform, adding 1g of dibutyl phthalate, and heating the mixture in water bath at 80 ℃ for 2h to obtain a product a; praseodymium nitrate is prepared into a praseodymium nitrate solution with the concentration of 1.5 wt%. Mixing 200mL of the obtained product a with 40mL of praseodymium nitrate solution, then adding 2g of glutaraldehyde, placing on a magnetic stirrer for full reaction for 14h, filtering by qualitative filter paper after the reaction is finished, cleaning a filter cake by ultrapure water, drying after cleaning, grinding into powder, sieving by a 100-mesh sieve to obtain a defluorinating agent, and finally placing in a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 0.25mg/L, and the removal rate is 99.98%.
Example 7
100g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) of the mixed solution and 300mL of deionized water are mixed and stirred in a magnetic stirrer overnight to obtain a uniform solution, 1g of phosphorylase is added into the solution to perform catalytic reaction for 50min at normal temperature, then liquid paraffin is added to perform stirring until the solution is uniform, 6g of polyethylene glycol is added, and the mixture is heated in water bath at 70 ℃ for 3h to obtain a product a; cerium nitrate was prepared into a cerium nitrate solution having a concentration of 1.5 wt%. Mixing 250mL of the obtained product a with 200mL of cerium nitrate solution, then adding 2g of glutaraldehyde, placing on a magnetic stirrer for full reaction for 10h, filtering by qualitative filter paper after the reaction is finished, cleaning a filter cake by ultrapure water, drying after cleaning, grinding into powder, sieving by a 100-mesh sieve to obtain a defluorinating agent, and finally placing in a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 0.24mg/L, and the removal rate is 99.98%.
Example 8
100g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) of the mixed solution and 300mL of deionized water, stirring the mixed solution in a magnetic stirrer overnight to obtain a uniform solution, adding 2g of phosphorylase into the solution to perform catalytic reaction for 60min at normal temperature, then adding liquid paraffin to stir the solution until the solution is uniform, adding 5g of polyethylene glycol, and heating the solution in water bath at 80 ℃ for 1h to obtain a product a; lanthanum nitrate is prepared into a lanthanum nitrate solution with the concentration of 2 wt%. Mixing 250mL of the obtained product a with 200mL of lanthanum nitrate solution, then adding 4g of epoxy chloropropane, placing on a magnetic stirrer for full reaction for 16h, filtering by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying after cleaning, grinding into powder, sieving by using a 100-mesh sieve to obtain a defluorinating agent, and finally placing in a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 0.16mg/L, and the removal rate is 99.99%.
Comparative example 1
100g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) and 300mL of deionized water, stirring overnight in a magnetic stirrer to obtain a uniform solution, adding 5g of dibutyl phthalate, and heating in a water bath at 70 ℃ for 2 hours to obtain a product a; lanthanum nitrate was prepared as a 1.5 wt% lanthanum nitrate solution. Mixing 300mL of the obtained product a with 100mL of lanthanum nitrate solution, adding 5g of epoxy chloropropane, placing on a magnetic stirrer for full reaction for 13h, filtering by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying after cleaning, grinding into powder, sieving by using a 100-mesh sieve to obtain a defluorinating agent, and finally placing in a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, and obtaining effluent with the fluorine content of 537mg/L and the removal rate of 57.07%.
Comparative example 2
100g of thermoplastic starch (density: 1.2 g/cm) was taken3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3%) and 300mL of deionized water and stirring overnight in a magnetic stirrer to obtain a uniform solution, thus obtaining a product a; lanthanum nitrate was prepared as a 1.5 wt% lanthanum nitrate solution. Mixing 300mL of the obtained product a with 100mL of lanthanum nitrate solution, adding 5g of epoxy chloropropane, placing on a magnetic stirrer for full reaction for 13h, filtering by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying after cleaning, grinding into powder, sieving by using a 100-mesh sieve to obtain a defluorinating agent, and finally placing in a dryer for storage for later use.
Treating fluorine in chemical wastewater, wherein the fluorine content in the wastewater is 1251mg/L, adding a fluorine removal agent and the wastewater into the fluorine-containing wastewater according to the mass ratio of 1:500, stirring for 15min, wherein the fluorine content in effluent is 1003mg/L, and the removal rate is 19.82%.
From the above results, it is understood that the fluorine removing agent of the present invention (examples 1 to 8) has a remarkable fluorine removing effect, a removal rate of 99.99%, a small amount of the fluorine removing agent and a short treatment time, as compared with comparative examples 1 to 2. The difference between examples 1 to 8 and comparative examples 1 to 2 is that comparative example 1 lacks the action of phosphorylase and liquid paraffin on thermoplastic starch, while comparative example 2 lacks both phosphorylase and liquid paraffin and the action of pore-forming agent on thermoplastic starch, and it is understood that the fluorine-removing effect of the fluorine-removing agent obtained in the absence of phosphorylase and liquid paraffin is significantly lower than that of the fluorine-removing agent obtained by the method of the present invention, although the fluorine-removing effect is significantly higher in the presence of pore-forming agent (comparative example 1) than in the absence of pore-forming agent (comparative example 2). Therefore, the activity of the thermoplastic starch can be obviously improved through the catalytic and activating effects of phosphorylase and liquid paraffin on the thermoplastic starch, so that the fluorine removal effect of the fluorine removal agent obtained after the fluorine removal agent is crosslinked with rare earth ions is excellent.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a fluorine removal agent comprises the following steps:
(1) mixing thermoplastic starch with deionized water, stirring overnight in a magnetic stirrer to obtain a uniform solution, adding phosphorylase into the solution, carrying out catalytic reaction for 30-60 min at normal temperature, then adding liquid paraffin, stirring until the solution is uniform, adding a pore-forming agent, and heating in a water bath at 60-80 ℃ for 1-3 h to obtain a product a;
preparing rare earth salt into a rare earth salt solution with a certain concentration;
(2) mixing the obtained product a with a rare earth ion solution, adding a cross-linking agent, placing the mixture on a magnetic stirrer to fully react for 10-16 h, filtering the mixture by using qualitative filter paper after the reaction is finished, cleaning a filter cake by using ultrapure water, drying the cleaned filter cake, grinding the powder, sieving the powder by using a 100-mesh sieve to obtain a fluorine removal agent, and finally placing the fluorine removal agent into a dryer to be stored for later use.
2. The method of manufacturing according to claim 1, wherein the thermoplastic starch has a density: 1.2g/cm3The melt index: 1-3 g/10min (190 ℃/2.16kg), volatile matter<0.3％。
3. The preparation method of claim 1, wherein the thermoplastic starch is mixed with deionized water in a ratio of 2-5 ml of deionized water per 1g of thermoplastic starch.
4. The production method according to claim 1, wherein the phosphorylase is added in an amount such that the mass ratio of the phosphorylase to the thermoplastic starch is 1: (50-100) is added.
5. The preparation method according to claim 1, wherein the pore former is selected from any one of dibutyl phthalate, polyethylene glycol or ethyl acetate.
6. The production method according to claim 1, wherein the rare earth salt is selected from nitrates of any one of the following groups: la, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
7. The method according to claim 1, wherein the concentration of the rare earth ion solution is 1 to 2 wt%.
8. The preparation method according to claim 1, wherein the product a and the rare earth ion solution are mixed in an amount of (1-10): 1 by volume ratio.
9. The production method according to claim 1, wherein the crosslinking agent is epichlorohydrin or glutaraldehyde.
10. A fluorine removing agent prepared by the method according to any one of claims 1 to 9.
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