WO2012024911A1 - Procédé pour la régénération d'un matériau filtrant utilisé dans l'élimination du fluor de l'eau potable - Google Patents

Procédé pour la régénération d'un matériau filtrant utilisé dans l'élimination du fluor de l'eau potable Download PDF

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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
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English (en)
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/fr
Priority to ZA2012/04090A priority Critical patent/ZA201204090B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

L'invention porte sur un procédé pour la régénération d'un matériau filtrant utilisé dans l'élimination du fluor de l'eau potable. Le procédé comprend le fait de soumettre le matériau filtrant granulaire constitué d'hydroxyapatite saturé d'ions fluorures à un traitement de régénération thermique et un traitement d'attrition mécanique alternés, le traitement d'attrition mécanique étant effectué lorsque l'efficacité de régénération devient plus faible après une pluralité de traitements de régénération thermique, afin que la surface fraîche des granulés d'hydroxyapatite soit exposée pour une récupération supplémentaire du pouvoir d'élimination du fluor. Le procédé a une efficacité de régénération élevée et peut être effectué de façon commode et le matériau filtrant régénéré a une stabilité de longue durée.
PCT/CN2011/070799 2010-08-27 2011-01-30 Procédé pour la régénération d'un matériau filtrant utilisé dans l'élimination du fluor de l'eau potable Ceased WO2012024911A1 (fr)

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 (zh) 2010-08-27 2010-08-27 一种饮用水除氟滤料的再生方法
CN201010264606.8 2010-08-27

Publications (1)

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

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CN (1) CN101912773B (fr)
WO (1) WO2012024911A1 (fr)
ZA (1) ZA201204090B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114735782A (zh) * 2022-05-06 2022-07-12 李宗洋 民用地下水除氟装置

Families Citing this family (7)

* Cited by examiner, † Cited by third party
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CN101912773B (zh) * 2010-08-27 2012-06-13 江苏永冠给排水设备有限公司 一种饮用水除氟滤料的再生方法
CN102728333B (zh) * 2012-07-09 2014-08-13 河海大学 一种除氟用球状羟基磷灰石再生装置
CN107324459B (zh) * 2017-07-31 2019-10-01 武汉理工大学 一种鱼骨炭除氟电极的制作方法
CN109179553B (zh) * 2018-09-25 2021-12-24 中煤科工集团杭州研究院有限公司 一种含氟废水除氟处理和滤料再生装置及方法
CN109395707A (zh) * 2018-11-07 2019-03-01 江苏永冠给排水设备有限公司 一种羟基磷灰石除氟滤料的再生方法
CN111471850B (zh) * 2020-05-20 2021-10-29 赣州有色冶金研究所有限公司 一种含氟钨渣洗涤过程的固氟方法
CN112958035B (zh) * 2021-03-31 2023-06-16 煤炭科学技术研究院有限公司 一种除氟滤料及其制备方法

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

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