WO2012024911A1 - Method for regenerating filter material used in removing fluorine from drinking water - Google Patents

Method for regenerating filter material used in removing fluorine from drinking water Download PDF

Info

Publication number
WO2012024911A1
WO2012024911A1 PCT/CN2011/070799 CN2011070799W WO2012024911A1 WO 2012024911 A1 WO2012024911 A1 WO 2012024911A1 CN 2011070799 W CN2011070799 W CN 2011070799W WO 2012024911 A1 WO2012024911 A1 WO 2012024911A1
Authority
WO
WIPO (PCT)
Prior art keywords
regeneration
filter material
hydroxyapatite
treatment
regeneration treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2011/070799
Other languages
French (fr)
Chinese (zh)
Inventor
刘泽山
冯莉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JIANGSU YONGGUAN WATER AND WASTEWATER EQUIPMENT CO Ltd
China University of Mining and Technology CUMT
China University of Mining and Technology Beijing CUMTB
Original Assignee
JIANGSU YONGGUAN WATER AND WASTEWATER EQUIPMENT CO Ltd
China University of Mining and Technology CUMT
China University of Mining and Technology Beijing CUMTB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JIANGSU YONGGUAN WATER AND WASTEWATER EQUIPMENT CO Ltd, China University of Mining and Technology CUMT, China University of Mining and Technology Beijing CUMTB filed Critical JIANGSU YONGGUAN WATER AND WASTEWATER EQUIPMENT CO Ltd
Publication of WO2012024911A1 publication Critical patent/WO2012024911A1/en
Priority to ZA2012/04090A priority Critical patent/ZA201204090B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/56—Use in the form of a bed
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

Definitions

  • the invention relates to a drinking water treatment technology, in particular to a method for regenerating a drinking water defluoridation filter material for granular hydroxyapatite.
  • Fluorosis caused by drinking high-fluorine water is a worldwide endemic disease. It causes fluorosis in the light, and causes fluorosis in the severe cases, causing osteoporosis, bone deformation, and even paralysis. China is one of the countries with the most serious fluorosis in the world. Except for Shanghai, it is distributed in all provinces of the country, mainly in rural and desert areas with relatively backward economy. At present, the population of sick villages with high fluoride water poisoning is as high as 81.41 million. The National Eleventh Five-Year Plan for Rural Drinking Water Safety Project decided to basically solve the drinking water safety problem of more than 300 million rural people by 2015.
  • the general fluorine removal technology at home and abroad mainly adopts the adsorption method, and the regeneration problem of the adsorbent is one of the key factors affecting whether the adsorbent material can be used for the fluorine removal filter.
  • Hydroxyapatite (HAP) is gradually recognized and accepted as a fluoride removal filter for drinking water.
  • the traditional regeneration method is mainly 0.25%. ⁇ 1%
  • the NaOH solution is used as a regenerant, and is neutralized with hydrochloric acid or sulfuric acid solution after regeneration.
  • the regeneration efficiency of the method is low, and the device has a corrosive effect, which affects the promotion and application of the hydroxyapatite defluoridation agent.
  • the coating regeneration method needs to return the HAP saturated with fluoride ions back to a solution consisting of a certain concentration of Ca2+ and H2PO3-, and adjust the pH of the solution to about 3, and re-react on the surface to form a new layer of hydroxyphosphorus. Graystone to restore its ability to remove fluorine. For the vast rural areas, this kind of operation is relatively complicated, and the reaction conditions are not easy to control, which makes it difficult to guarantee the regeneration efficiency.
  • the object of the present invention is to provide a method for regenerating a drinking water defluoridation filter material, which realizes high efficiency of regeneration of hydroxyapatite filter material by coupling of thermal regeneration and mechanical wear, no need to replace filter material, convenient use, and simple method. Fast.
  • the regeneration method of the present invention is as follows: a, using thermal regeneration treatment: the hydroxyapatite granular filter material saturated with fluoride ions is heated in water for a period of time, and can be reused until it is again saturated with fluoride ions; b. Re-recycling the granular hydroxyapatite filter material saturated with fluoride ions again; c, repeat step b, perform multiple thermal regeneration treatment until the regeneration rate of hydroxyapatite is less than 20%; d.
  • Mechanical wear regeneration treatment the hydroxyapatite granular filter material saturated with fluoride ions with a regeneration rate of less than 20% is used in the fluorine removal device, and the fluoroapatite is worn away by the water flow to remove the hydroxyapatite.
  • the outer layer reveals a fresh surface, restores the fluorine removal ability of the hydroxyapatite, and replenishes the new filter material corresponding to the corresponding amount of wear; e, then use the thermal regeneration treatment method, repeat steps c and d, recycle the thermal regeneration treatment multiple times, mechanical wear regeneration once, can achieve the reuse of the fluorine removal filter; through thermal regeneration treatment and mechanical wear regeneration The treatment is used alternately to maximize the filter regeneration efficiency and cycle times.
  • the filter material is heated in water at a temperature of 50 to 100 ° for a duration of 0.5 to 5 hours; and the number of repeated use of the thermal regeneration treatment is about 5 times.
  • the regeneration method of the present invention achieves the maximum of regeneration efficiency and repeated use by alternately treating the thermal regeneration treatment and mechanical wear of the hydroxyapatite granular filter material saturated with fluoride ions, thereby realizing the hydroxyapatite filter material.
  • the regeneration is highly efficient. After repeated heat regeneration treatment, the mechanical wear treatment is used when the regeneration rate is low, so that the fresh surface of the hydroxyapatite pellet is exposed, the fluorine removal ability is restored, and the new material is added according to the wear amount to ensure the fluorine removal ability, instead of Wait until the filter material is completely effective after removing the fluorine performance.
  • the main advantages are: 1.
  • the regeneration efficiency of the fluorine removal filter is high: the single regeneration efficiency is greater than 50% to 80%; 2.
  • the fluorine removal filter material is continuously updated during the operation, and the fluorine removal performance is stable for a long time. 3.
  • the regeneration method is simple and easy.
  • thermal regeneration treatment is adopted: by using a heating method to provide energy for removing the fluorine-containing filter material to obtain energy of the hydroxyapatite saturated with fluorine ions, the fluorine ions on the surface of the hydroxyapatite migrate to the inside, and the surface The active position is vacated and the fluorine removal ability is restored; By loading the container for removing the fluorine filter, the granular filter material saturated with fluoride ions is heated to 95° in water for 0.5 hour, and then can be used continuously;
  • Q is the regeneration defluoridation capacity mg/g
  • Co is the concentration of fluoride ion in the raw water mg/L
  • C is the concentration of fluoride ion in the water after saturation adsorption of the regenerated defluorinated filter material, mg/L
  • V is the water sample volume L
  • m is the mass g of the fluorine-containing granular filter.
  • the granular hydroxyapatite filter material saturated with fluoride ions is heated to 95° for 0.5 hours, and can be used continuously.
  • the regeneration rate at this time can be measured by the same method as above. %;
  • step c repeat the process of step b, after 5 times of thermal regeneration, mechanical wear regeneration treatment is required, and the measured regeneration rate is reduced to 19%;
  • the second embodiment is basically the same as the first embodiment, the same parts are omitted, and the different parts are as follows:
  • the granular filter material saturated with fluoride ions is heated to 50 ° in water, and can continue to be used after 5 hours, at which time the measured regeneration rate is 55%;
  • the granular hydroxyapatite filter material saturated with fluoride ions is heated to 50°, and can be used continuously after 5 hours, and the measured regeneration rate is 45%;
  • step c repeat the process of step b, after 5 times of thermal regeneration, mechanical wear regeneration treatment is required, and the measured regeneration rate is reduced to 18%;
  • the method of the thermal regeneration treatment is repeated, and the steps c and d are repeated, and after the thermal regeneration treatment is cycled for about 5 times, the mechanical abrasion is regenerated once, and the recycling of the fluorine-removing filter material can be realized.
  • the third embodiment is basically the same as the first embodiment, the same parts are omitted, and the different parts are as follows:
  • the granular filter material saturated with fluoride ions is heated to 70 ° in water, and can continue to be used after 3 hours, at which time the measured regeneration rate is 65%;
  • the granular hydroxyapatite filter material saturated with fluoride ions is heated to 70° for 3 hours, and the measured regeneration rate is 55%;
  • step c repeat the process of step c, after 5 times of thermal regeneration, mechanical wear regeneration treatment is required, and the measured regeneration rate is reduced to 19%;
  • the method of the thermal regeneration treatment is repeated, and the steps c and d are repeated, and after the thermal regeneration treatment is cycled for about 5 times, the mechanical abrasion is regenerated once, and the recycling of the fluorine-removing filter material can be realized.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

A method for regenerating filter material used in removing fluorine from drinking water is provided. The method comprises subjecting the granular filter material of hydroxyapatite saturated with fluoride ion to alternate thermal regeneration treatment and mechanical attrition treatment, wherein the mechanical attrition treatment will be carried out when the regeneration efficiency becomes lower after a plurality of thermal regeneration treatment, so that the fresh surface of the hydroxyapatite granules is exposed for further recovery of fluorine removal capability. The method has high regeneration efficiency and can be performed conveniently, and the regenerated filter material has long term stability.

Description

一种饮用水除氟滤料的再生方法  Method for regenerating drinking water defluoridation filter 技术领域Technical field

本发明涉及一种饮用水处理技术，尤其适用于粒状羟基磷灰石的饮用水除氟滤料的再生方法。 The invention relates to a drinking water treatment technology, in particular to a method for regenerating a drinking water defluoridation filter material for granular hydroxyapatite.

背景技术Background technique

饮用高氟水造成的氟中毒是涉及世界范围的地方病，轻者引起氟斑牙，重者会引起氟骨症，造成骨质疏松、骨变形，甚至瘫痪，丧失劳动能力。中国是世界上氟中毒最严重的国家之一，除上海市外，遍布全国各省，主要分布在经济相对落后的农村和牧区，目前因高氟水源中毒的病村人口高达8141万。《全国农村饮水安全工程“十一五”规划》决定到2015年基本解决3亿多农村人口的饮水安全问题。Fluorosis caused by drinking high-fluorine water is a worldwide endemic disease. It causes fluorosis in the light, and causes fluorosis in the severe cases, causing osteoporosis, bone deformation, and even paralysis. China is one of the countries with the most serious fluorosis in the world. Except for Shanghai, it is distributed in all provinces of the country, mainly in rural and pastoral areas with relatively backward economy. At present, the population of sick villages with high fluoride water poisoning is as high as 81.41 million. The National Eleventh Five-Year Plan for Rural Drinking Water Safety Project decided to basically solve the drinking water safety problem of more than 300 million rural people by 2015.

目前，国内外通用除氟技术主要采用吸附法，而吸附剂的再生问题是影响吸附材料能否用于除氟滤料的关键因素之一。羟基磷灰石（HAP）作为饮用水除氟滤料正在逐渐被人们所认识和接受，其传统的再生方法主要是用0.25％ ～1％ 的NaOH溶液作为再生剂，再生后用盐酸或硫酸溶液中和，该法再生效率低，对设备有腐蚀作用，影响了羟基磷灰石降氟剂的推广和应用。应波，李新云，丛正茂在“饮水降氟材料—羟基磷灰石的再生方法的研究” （卫生研究, 2002, 31(02): 83-84）一文中报道了羟基磷灰石的NaOH再生法与表面涂层再生法的再生效果比较，结果表明，用表面涂层再生法对饱和的羟基磷灰石进行再生处理，其再生效率可达46 ％－64 ％，与传统的NaOH再生法相比，再生效率提高了2倍以上。但涂层再生法需要将已被氟离子饱和的HAP放回到由一定浓度Ca2+和H2PO3-组成的溶液中，并调整溶液pH值为3左右，在其表面重新反应生成一层新的羟基磷灰石，以恢复其除氟能力。对于广大农村地区来说，这种操作相对复杂，反应条件不易控制，从而容易造成再生效率难以保证。At present, the general fluorine removal technology at home and abroad mainly adopts the adsorption method, and the regeneration problem of the adsorbent is one of the key factors affecting whether the adsorbent material can be used for the fluorine removal filter. Hydroxyapatite (HAP) is gradually recognized and accepted as a fluoride removal filter for drinking water. The traditional regeneration method is mainly 0.25%. ~1% The NaOH solution is used as a regenerant, and is neutralized with hydrochloric acid or sulfuric acid solution after regeneration. The regeneration efficiency of the method is low, and the device has a corrosive effect, which affects the promotion and application of the hydroxyapatite defluoridation agent. Ying Bo, Li Xinyun, Cong Zhengmao, “Study on the Regeneration Method of Drinking Water Defluoridation Material-Hydroxyapatite” (Health Research, 2002, 31(02): 83-84) reported the comparison of the regeneration effect of hydroxyapatite NaOH regeneration method and surface coating regeneration method. The results show that the regeneration of hydroxyapatite is regenerated by surface coating regeneration method. Up to 46 %-64 %, compared with the traditional NaOH regeneration method, the regeneration efficiency is increased by more than 2 times. However, the coating regeneration method needs to return the HAP saturated with fluoride ions back to a solution consisting of a certain concentration of Ca2+ and H2PO3-, and adjust the pH of the solution to about 3, and re-react on the surface to form a new layer of hydroxyphosphorus. Graystone to restore its ability to remove fluorine. For the vast rural areas, this kind of operation is relatively complicated, and the reaction conditions are not easy to control, which makes it difficult to guarantee the regeneration efficiency.

由于除氟滤料的使用寿命都较短，在除氟滤料不能再生时，需要整体更换滤料，更换过程非常麻烦，是导致很多除氟设备不能长期使用的一个重要原因。Since the service life of the fluorine removal filter material is short, when the fluorine removal filter material cannot be regenerated, the filter material needs to be replaced as a whole, and the replacement process is very troublesome, which is an important reason that many fluorine removal equipment cannot be used for a long time.

技术问题technical problem

本发明的目的是提供一种饮用水除氟滤料的再生方法，通过热再生和机械磨损的耦合，实现羟基磷灰石滤料再生高效率、滤料无需更换、使用方便、方法简单易行、快捷。 The object of the present invention is to provide a method for regenerating a drinking water defluoridation filter material, which realizes high efficiency of regeneration of hydroxyapatite filter material by coupling of thermal regeneration and mechanical wear, no need to replace filter material, convenient use, and simple method. Fast.

技术解决方案Technical solution

本发明的再生方法如下：
a、采用热再生处理：对已被氟离子饱和的羟基磷灰石粒状滤料在水中加热，持续一段时间，即可重新使用至再次被氟离子饱和；
b、对再次被氟离子饱和的粒状羟基磷灰石滤料再次进行热再生处理；
c、重复步骤b，进行多次热再生处理，直至羟基磷灰石的再生率低于20%；
d、采用机械磨损再生处理：使再生率低于20%的被氟离子饱和的羟基磷灰石粒状滤料在除氟装置内，通过水流使得除氟滤料运动磨损，磨去羟基磷灰石的外层，露出新鲜表面，恢复羟基磷灰石的除氟能力，补充相应磨损量的新滤料即可重新使用；
e、之后再使用热再生处理的方法，重复步骤c和d，循环使用热再生处理多次，机械磨损再生1次，即可实现除氟滤料的重复利用；通过热再生处理与机械磨损再生处理交替使用，达到滤料再生效率和循环使用次数的最大化。The regeneration method of the present invention is as follows:
a, using thermal regeneration treatment: the hydroxyapatite granular filter material saturated with fluoride ions is heated in water for a period of time, and can be reused until it is again saturated with fluoride ions;
b. Re-recycling the granular hydroxyapatite filter material saturated with fluoride ions again;
c, repeat step b, perform multiple thermal regeneration treatment until the regeneration rate of hydroxyapatite is less than 20%;
d. Mechanical wear regeneration treatment: the hydroxyapatite granular filter material saturated with fluoride ions with a regeneration rate of less than 20% is used in the fluorine removal device, and the fluoroapatite is worn away by the water flow to remove the hydroxyapatite. The outer layer reveals a fresh surface, restores the fluorine removal ability of the hydroxyapatite, and replenishes the new filter material corresponding to the corresponding amount of wear;
e, then use the thermal regeneration treatment method, repeat steps c and d, recycle the thermal regeneration treatment multiple times, mechanical wear regeneration once, can achieve the reuse of the fluorine removal filter; through thermal regeneration treatment and mechanical wear regeneration The treatment is used alternately to maximize the filter regeneration efficiency and cycle times.

所述滤料在水中加热的温度为50～100°，持续时间为0.5～5小时；所述重复使用热再生处理的次数约为5次。The filter material is heated in water at a temperature of 50 to 100 ° for a duration of 0.5 to 5 hours; and the number of repeated use of the thermal regeneration treatment is about 5 times.

有益效果Beneficial effect

本发明的再生方法，通过对被氟离子饱和的羟基磷灰石粒状滤料的热再生处理和机械磨损的交替处理，达到再生效率和重复使用次数的极大化，实现羟基磷灰石滤料的再生高效率。经过多次热再生处理后，再生率较低时采用机械磨损处理，从而使得羟基磷灰石小球的新鲜表面暴露，除氟能力得以恢复，并根据磨损量添加新料，保证除氟能力，而不是等到滤料除氟性能实效后全部更新。主要优点在于：
1、除氟滤料再生效率高：单次再生效率大于50%～80%；
2、除氟滤料在运行过程中不断更新，除氟性能长期稳定。
3、再生方法简单易行。The regeneration method of the present invention achieves the maximum of regeneration efficiency and repeated use by alternately treating the thermal regeneration treatment and mechanical wear of the hydroxyapatite granular filter material saturated with fluoride ions, thereby realizing the hydroxyapatite filter material. The regeneration is highly efficient. After repeated heat regeneration treatment, the mechanical wear treatment is used when the regeneration rate is low, so that the fresh surface of the hydroxyapatite pellet is exposed, the fluorine removal ability is restored, and the new material is added according to the wear amount to ensure the fluorine removal ability, instead of Wait until the filter material is completely effective after removing the fluorine performance. The main advantages are:
1. The regeneration efficiency of the fluorine removal filter is high: the single regeneration efficiency is greater than 50% to 80%;
2. The fluorine removal filter material is continuously updated during the operation, and the fluorine removal performance is stable for a long time.
3. The regeneration method is simple and easy.

本发明的实施方式Embodiments of the invention

实施例一、Embodiment 1

a、首先采用热再生处理：利用加热的方式，提供除氟滤料以能量，使已被氟离子饱和的羟基磷灰石获得能量后，羟基磷灰石表面的氟离子向内部迁移，表面的活性位置空出来，除氟能力得以恢复； 通过装放除氟滤料的容器，对已被氟离子饱和的粒状滤料在水中加热至95°，持续0.5h后，即可继续使用；a. Firstly, thermal regeneration treatment is adopted: by using a heating method to provide energy for removing the fluorine-containing filter material to obtain energy of the hydroxyapatite saturated with fluorine ions, the fluorine ions on the surface of the hydroxyapatite migrate to the inside, and the surface The active position is vacated and the fluorine removal ability is restored; By loading the container for removing the fluorine filter, the granular filter material saturated with fluoride ions is heated to 95° in water for 0.5 hour, and then can be used continuously;

依据是：假如在容器中放入一定质量（m）的再生除氟粒状滤料，向内加入含氟水，含氟水的体积(v)为将再生除氟滤料完全浸泡为准，然后振荡容器，使再生除氟滤料达到吸附氟离子饱和后，采用氟离子电极测试水中含氟离子的浓度（按照GB7484-87水质-氟化物的测定方法-离子选择电极法），利用公式Q=V*(C0-C)/m计算出再生除氟容量，用再生除氟容量除以再生前的除氟滤料的除氟容量，得出再生率为50%；The basis is: if a certain mass (m) of regenerated defluorinated granular filter material is placed in the container, fluorine-containing water is added inward, and the volume (v) of the fluorine-containing water is completely immersed in the regenerated defluorinated filter material, and then After oscillating the container, the regenerated defluorination filter material is saturated with the adsorbed fluoride ion, and the fluoride ion electrode is used to test the concentration of the fluoride ion in the water (according to GB7484-87 water quality-fluoride determination method-ion selective electrode method), using the formula Q= V*(C 0 -C)/m is used to calculate the regeneration defluoridation capacity, and the regeneration defluorination capacity is divided by the defluorination capacity of the defluorination filter material before regeneration, and the regeneration rate is 50%;

式中Q为再生除氟容量mg/g，Co为原水中氟离子的浓度mg/L，C为再生除氟滤料饱和吸附之后水中氟离子的浓度mg/L，V为水样体积L，m为除氟粒状滤料的质量g。Where Q is the regeneration defluoridation capacity mg/g, Co is the concentration of fluoride ion in the raw water mg/L, C is the concentration of fluoride ion in the water after saturation adsorption of the regenerated defluorinated filter material, mg/L, and V is the water sample volume L, m is the mass g of the fluorine-containing granular filter.

b、使用一段时间后，将再次被氟离子饱和的粒状羟基磷灰石滤料加热至95°，持续0.5h后即可继续使用，用上述同样的方法可测出此时的再生率为40%；b. After using for a period of time, the granular hydroxyapatite filter material saturated with fluoride ions is heated to 95° for 0.5 hours, and can be used continuously. The regeneration rate at this time can be measured by the same method as above. %;

c、重复步骤b的过程，热再生5次后，需进行机械磨损再生处理，此时测出的再生率降到19%；c, repeat the process of step b, after 5 times of thermal regeneration, mechanical wear regeneration treatment is required, and the measured regeneration rate is reduced to 19%;

d、机械磨损再生处理：通过水流使得除氟滤料在除氟装置内运动，造成已被氟离子饱和的粒状羟基磷灰石的机械磨损；从而使得羟基磷灰石小球的新鲜表面暴露，除氟能力得以恢复；用与步骤b同样的方法测定此时再生率达80%；将磨损后的粒状滤料过滤、洗涤，然后将滤液蒸发、称重，得到粒状滤料的磨损量，一般一次磨损量约为投药量的10%，补充相应磨损量的新滤料；d. Mechanical wear regeneration treatment: the movement of the fluorine removal filter in the fluorine removal device through the water flow causes mechanical wear of the granular hydroxyapatite which has been saturated with fluoride ions; thereby exposing the fresh surface of the hydroxyapatite pellet to remove fluorine The ability is restored; the regeneration rate is determined to be 80% in the same manner as in step b; the worn granular filter material is filtered and washed, and then the filtrate is evaporated and weighed to obtain a wear amount of the granular filter material, which is generally worn once. The amount of the new filter material is about 10% of the dosage, supplementing the corresponding amount of wear;

e、之后再使用热再生处理的方法，重复步骤c和d，循环使用热再生处理约5次后，机械磨损再生1次，即可实现除氟滤料的重复利用；通过热再生处理与机械磨损再生处理交替使用，达到滤料再生效率和循环使用次数的最大化。e, after using the thermal regeneration treatment method, repeat steps c and d, recycle the thermal regeneration treatment about 5 times, mechanical wear regeneration once, can achieve the reuse of the fluorine removal filter; through thermal regeneration treatment and machinery The wear regeneration treatment is used alternately to maximize the filter regeneration efficiency and cycle times.

实施例二、与实施例一基本相同，相同部分略，不同部分如下：The second embodiment is basically the same as the first embodiment, the same parts are omitted, and the different parts are as follows:

a、首先采用热再生处理：对已被氟离子饱和的粒状滤料在水中加热至50°，持续5h后即可继续使用，此时测出的再生率为55%；a, first using thermal regeneration treatment: the granular filter material saturated with fluoride ions is heated to 50 ° in water, and can continue to be used after 5 hours, at which time the measured regeneration rate is 55%;

b、使用一段时间后，将再次被氟离子饱和的粒状羟基磷灰石滤料加热至50°，持续5h后即可继续使用，此时测出的再生率为45%；b. After using for a period of time, the granular hydroxyapatite filter material saturated with fluoride ions is heated to 50°, and can be used continuously after 5 hours, and the measured regeneration rate is 45%;

c、重复步骤b的过程，热再生5次后，需进行机械磨损再生处理，此时测出的再生率降到18%；c, repeat the process of step b, after 5 times of thermal regeneration, mechanical wear regeneration treatment is required, and the measured regeneration rate is reduced to 18%;

d、机械磨损再生处理：测定此时再生率达80%；磨损量约为投药量的10%，补充相应磨损量的新滤料；d. Mechanical wear regeneration treatment: the regeneration rate is determined to be 80% at this time; the wear amount is about 10% of the dosage, and the new filter material corresponding to the wear amount is supplemented;

e、之后再使用热再生处理的方法，重复步骤c和d，循环使用热再生处理约5次后，机械磨损再生1次，即可实现除氟滤料的重复利用。e. Thereafter, the method of the thermal regeneration treatment is repeated, and the steps c and d are repeated, and after the thermal regeneration treatment is cycled for about 5 times, the mechanical abrasion is regenerated once, and the recycling of the fluorine-removing filter material can be realized.

实施例三、与实施例一基本相同，相同部分略，不同部分如下：The third embodiment is basically the same as the first embodiment, the same parts are omitted, and the different parts are as follows:

a、首先采用热再生处理：对已被氟离子饱和的粒状滤料在水中加热至70°，持续3h后即可继续使用，此时测出的再生率为65%；a, first using thermal regeneration treatment: the granular filter material saturated with fluoride ions is heated to 70 ° in water, and can continue to be used after 3 hours, at which time the measured regeneration rate is 65%;

b、使用一段时间后，将再次被氟离子饱和的粒状羟基磷灰石滤料加热至70°，持续3h，此时测出的再生率为55%；b. After using for a period of time, the granular hydroxyapatite filter material saturated with fluoride ions is heated to 70° for 3 hours, and the measured regeneration rate is 55%;

c、重复步骤c的过程，热再生5次后，需进行机械磨损再生处理，此时测出的再生率降到19%；c, repeat the process of step c, after 5 times of thermal regeneration, mechanical wear regeneration treatment is required, and the measured regeneration rate is reduced to 19%;

d、机械磨损再生处理：测定此时再生率达80%；磨损量约为投药量的10%，补充相应磨损量的新滤料；d. Mechanical wear regeneration treatment: the regeneration rate is determined to be 80% at this time; the wear amount is about 10% of the dosage, and the new filter material corresponding to the wear amount is supplemented;

e、之后再使用热再生处理的方法，重复步骤c和d，循环使用热再生处理约5次后，机械磨损再生1次，即可实现除氟滤料的重复利用。e. Thereafter, the method of the thermal regeneration treatment is repeated, and the steps c and d are repeated, and after the thermal regeneration treatment is cycled for about 5 times, the mechanical abrasion is regenerated once, and the recycling of the fluorine-removing filter material can be realized.

Claims (3)

一种饮用水除氟滤料的再生方法，其特征在于： A method for regenerating a drinking water defluoridation filter material, characterized in that: a、采用热再生处理：对已被氟离子饱和的羟基磷灰石粒状滤料在水中加热，持续一段时间，即可重新使用至再次被氟离子饱和；a, using thermal regeneration treatment: the hydroxyapatite granular filter material saturated with fluoride ions is heated in water for a period of time, and can be reused until it is again saturated with fluoride ions; b、对再次被氟离子饱和的粒状羟基磷灰石滤料再次进行热再生处理；b. Re-recycling the granular hydroxyapatite filter material saturated with fluoride ions again; c、重复步骤b，进行多次热再生处理，直至羟基磷灰石的再生率低于20%；c, repeat step b, perform multiple thermal regeneration treatment until the regeneration rate of hydroxyapatite is less than 20%; d、采用机械磨损再生处理：使再生率低于20%的被氟离子饱和的羟基磷灰石粒状滤料在除氟装置内，通过水流使得除氟滤料运动磨损，磨去羟基磷灰石的外层，露出新鲜表面，恢复羟基磷灰石的除氟能力，补充相应磨损量的新滤料即可重新使用；d. Mechanical wear regeneration treatment: the hydroxyapatite granular filter material saturated with fluoride ions with a regeneration rate of less than 20% is used in the fluorine removal device, and the fluoroapatite is worn away by the water flow to remove the hydroxyapatite. The outer layer reveals a fresh surface, restores the fluorine removal ability of the hydroxyapatite, and replenishes the new filter material corresponding to the corresponding amount of wear; e、之后再使用热再生处理的方法，重复步骤c和d，循环使用热再生处理多次，机械磨损再生1次，即可实现除氟滤料的重复利用；通过热再生处理与机械磨损再生处理交替使用，达到滤料再生效率和循环使用次数的最大化。 e, then use the thermal regeneration treatment method, repeat steps c and d, recycle the thermal regeneration treatment multiple times, mechanical wear regeneration once, can achieve the reuse of the fluorine removal filter; through thermal regeneration treatment and mechanical wear regeneration The treatment is used alternately to maximize the filter regeneration efficiency and cycle times. 根据权利要求1所述的一种饮用水除氟滤料的再生方法，其特征在于：所述滤料在水中加热的温度为50～100°，持续时间为0.5～5小时。The method for regenerating a drinking water defluoridation filter according to claim 1, wherein the filter material is heated in water at a temperature of 50 to 100 ° for a duration of 0.5 to 5 hours. 根据权利要求1所述的一种饮用水除氟滤料的再生方法，其特征在于：所述重复使用热再生处理的次数约为5次。A method for regenerating a drinking water defluoridation filter according to claim 1, wherein the number of times of reusing the heat regeneration treatment is about 5 times.
PCT/CN2011/070799 2010-08-27 2011-01-30 Method for regenerating filter material used in removing fluorine from drinking water Ceased WO2012024911A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
ZA2012/04090A ZA201204090B (en) 2010-08-27 2012-06-05 Method for regenerating filter material used in removing fluorine from drinking water

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 201010264606 CN101912773B (en) 2010-08-27 2010-08-27 Regenerating method of drinking water defluoridation filtering material
CN201010264606.8 2010-08-27

Publications (1)

Publication Number Publication Date
WO2012024911A1 true WO2012024911A1 (en) 2012-03-01

Family

ID=43320498

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2011/070799 Ceased WO2012024911A1 (en) 2010-08-27 2011-01-30 Method for regenerating filter material used in removing fluorine from drinking water

Country Status (3)

Country Link
CN (1) CN101912773B (en)
WO (1) WO2012024911A1 (en)
ZA (1) ZA201204090B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114735782A (en) * 2022-05-06 2022-07-12 李宗洋 Civil underground water defluorination device

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101912773B (en) * 2010-08-27 2012-06-13 江苏永冠给排水设备有限公司 Regenerating method of drinking water defluoridation filtering material
CN102728333B (en) * 2012-07-09 2014-08-13 河海大学 Device for regenerating spherical hydroxyapatite for defluorination
CN107324459B (en) * 2017-07-31 2019-10-01 武汉理工大学 A kind of production method that fish-bone charcoal removes fluoride electrode
CN109179553B (en) * 2018-09-25 2021-12-24 中煤科工集团杭州研究院有限公司 Fluorine-containing wastewater defluorination treatment and filter material regeneration device and method
CN109395707A (en) * 2018-11-07 2019-03-01 江苏永冠给排水设备有限公司 A kind of regeneration method of hydroxyapatite defluoridation filter material
CN111471850B (en) * 2020-05-20 2021-10-29 赣州有色冶金研究所有限公司 Fluorine fixing method for fluorine-containing tungsten slag washing process
CN112958035B (en) * 2021-03-31 2023-06-16 煤炭科学技术研究院有限公司 Defluorination filter material and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1039567A (en) * 1988-07-22 1990-02-14 北京工业大学 The preparation method and use of calcium phosphate powder
CN1616145A (en) * 2003-11-11 2005-05-18 李书伟 Process for preparing high efficiency modified fluorine reducd water purifying filter material
JP2006242921A (en) * 2005-03-07 2006-09-14 Pentax Corp Metal ion removal method, adsorbent regeneration method, and adsorber regeneration method
US20060207940A1 (en) * 2005-03-07 2006-09-21 Tsuneo Okuyama Adsorbent, adsorption apparatus, and method for manufacturing the adsorption apparatus
CN101773817A (en) * 2009-01-13 2010-07-14 厦门绿邦膜技术有限公司 Composite absorption material for wastewater treatment and preparation method thereof
CN101912773A (en) * 2010-08-27 2010-12-15 江苏永冠给排水设备有限公司 A kind of regeneration method of drinking water defluoridation filter material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS586553B2 (en) * 1977-04-06 1983-02-04 安宅建設工業株式会社 Method for removing fluorine ions in water
CN2042078U (en) * 1988-12-16 1989-08-02 北京市永定门外粮库 Defluorination apparatus for natural geothermal mineral water
JP2003170003A (en) * 2001-11-30 2003-06-17 Jae Jong Kim Method for treating fluorine-containing fluid and device for treating fluorine-containing fluid
CN1415537A (en) * 2002-11-19 2003-05-07 武汉化工学院 Adulterated hydroxyapatite and its production method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1039567A (en) * 1988-07-22 1990-02-14 北京工业大学 The preparation method and use of calcium phosphate powder
CN1616145A (en) * 2003-11-11 2005-05-18 李书伟 Process for preparing high efficiency modified fluorine reducd water purifying filter material
JP2006242921A (en) * 2005-03-07 2006-09-14 Pentax Corp Metal ion removal method, adsorbent regeneration method, and adsorber regeneration method
US20060207940A1 (en) * 2005-03-07 2006-09-21 Tsuneo Okuyama Adsorbent, adsorption apparatus, and method for manufacturing the adsorption apparatus
CN101773817A (en) * 2009-01-13 2010-07-14 厦门绿邦膜技术有限公司 Composite absorption material for wastewater treatment and preparation method thereof
CN101912773A (en) * 2010-08-27 2010-12-15 江苏永冠给排水设备有限公司 A kind of regeneration method of drinking water defluoridation filter material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YING BO ET AL.: "Study on the Regeneration Methods of the Synthetic Hydroxyapatite as a Material for Defluoridation of Drinking Water.", JOURNAL OF HYGIENE RESEARCH., vol. 31, no. 2, April 2002 (2002-04-01), pages 83 - 84 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114735782A (en) * 2022-05-06 2022-07-12 李宗洋 Civil underground water defluorination device

Also Published As

Publication number Publication date
CN101912773B (en) 2012-06-13
ZA201204090B (en) 2013-02-27
CN101912773A (en) 2010-12-15

Similar Documents

Publication Publication Date Title
WO2012024911A1 (en) Method for regenerating filter material used in removing fluorine from drinking water
CN101549873B (en) Surface active agent modification zeolites, method of preparing thereof and usage
CN105381782A (en) Modified zeolite adsorbent for removing ammonia nitrogen and phosphate in water, and preparation and regeneration method thereof
CN111377497B (en) A kind of sodium alginate-embedded iron carbon-maifan stone high-efficiency phosphorus removal granules and preparation method thereof
CN114984956A (en) Preparation method of magnetic sludge biochar applied to activated peroxymonosulfate for efficiently degrading sulfamethoxazole in water
CN101723499B (en) Preparation Technology of Diethylene Triamine Pentaacetic Acid Modified Diatomite
CN105797679B (en) A kind of Zeolite modifying method of synchronous removal ammonia nitrogen in waste water and phosphate radical
CN103706326B (en) A kind of preparation method of natural minerals loaded nano defluorinating agent
CN107626335A (en) A kind of bismuth system/carbonitride composite catalyst and its preparation method and application
CN102527328A (en) A method for preparing an adsorption material for removing phosphate in sewage
CN110508232A (en) Preparation method and application of hydroxyapatite and method for removing uranium in wastewater by hydroxyapatite
CN102145239A (en) Preparation method of zeolite filter material for water purification
CN103071452B (en) Method for preparing lanthanum or cerium pillared montmorillonite fluorine removal agent
CN101554579B (en) In situ regeneration method for filler saturated in adsorbing phosphorus in artificial wetland
CN114682217A (en) Metal single-atom doped biomass carbon adsorption material, preparation method and application
CN101838042B (en) Preparation and regeneration method for water treatment defluoridation filter material based on natural mineral
CN110681344A (en) A new type of zirconium series nano-hybrid material and application method
CN102910700B (en) Method for removing phosphate in water through absorption of graphite oxide modified by zirconia
CN104591336B (en) A kind of from containing the method reclaiming phosphorus fosfomycin waste water
CN101088604A (en) Process of preparing filter material for reducing fluoride content and improving water quality
CN102962028B (en) Preparation method of heavy metal ion adsorbent
CN103570120B (en) A kind of preparation of cerium oxide changed red mud catalyzer and the application in water technology thereof
CN105056987B (en) A kind of preparation method of modified zeolite for catalysis oxidation
CN114797759B (en) A kind of hydroxyapatite/halloysite nanotube composite adsorption material and its preparation method and application
CN113000010B (en) A composite modification method of activated alumina for synergistic removal of nitrogen and phosphorus in building rainwater

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11819286

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1881/MUMNP/2012

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11819286

Country of ref document: EP

Kind code of ref document: A1