CN103706326A - Preparation method of natural mineral-loaded nanometer fluorine removal agent - Google Patents
Preparation method of natural mineral-loaded nanometer fluorine removal agent Download PDFInfo
- Publication number
- CN103706326A CN103706326A CN201310723159.1A CN201310723159A CN103706326A CN 103706326 A CN103706326 A CN 103706326A CN 201310723159 A CN201310723159 A CN 201310723159A CN 103706326 A CN103706326 A CN 103706326A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- zeolite
- preparation
- acid
- temperature
- 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.)
- Granted
Links
Images
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a natural mineral-loaded nanometer fluorine removal agent. The method comprises high-temperature activation treatment, acid activation treatment, alkali activation treatment and a metal salt reaction. Natural zeolite is high in mechanical strength and is full of fine holes and channels inside, and nanometer materials can be effectively fixed in the internal channels of the natural zeolite under a water flow condition when the natural zeolite is taken as a carrier of a nanometer fluorine removal material, so that the agglomeration and loss of the nanometer materials are avoided, and the fluorine adsorption capacity is increased. Moreover, the natural zeolite is reproducible, so that the fluorine removal cost is reduced. The fluorine removal agent with larger specific surface area can provide more active sites for realizing a high fluorine adsorption volume, and can be widely applied to the aspects of purification treatment of high-fluorine surface water and underground water, treatment of fluorine-containing sewage, and the like.
Description
Background technology
Fluorine is one of necessary trace element of human body, but takes the photograph fluorine amount human body day when excessive, will cause endemic fluorosis.Long-term drinking high-fluorine water, will cause fluorine poisoning, cause fluorine dental plaque and fluorosis of bone, gently cause that tooth goes bad, comes off, heavy cause osteosclerosis or osteoporosis, even paralyse, and cause people's disability.According to the investigation of the Ministry of Public Health, show, endemic fluorosis distributes very extensive in China, and most provinces have endemic fluorosis to exist.Therefore the fluorine of, effectively controlling and removing in water body is the important topic that is related to environment and human health.
China's endemic fluorosis is mainly divided into three kinds: a kind of is drinking water type fluorine poisoning, and this is one type that endemic area distribution is the widest, number of patients is maximum, is mainly distributed in the wide geographic area to the north of Huaihe River-Qinling Mountains-Kun Lun Mountain.The second is pollution that caused by coal burning type fluorine poisoning, is mainly distributed in each provinces and regions, south such as Yunnan, Guizhou, Sichuan, Hunan, Hubei, Guangxi, Chongqing.The third is drinking brick-tea type fluorosis, and distribution lesion is less, and number is also fewer.Drinking water type fluorine poisoning accounts for very large ratio as can be seen here, and the distribution of fluorine poisoning and harmfulness are all very large.At present main reducing fluoride method has ion-exchange, absorption method, electroosmose process and hyperfiltration etc.Wherein absorption method is in water treatment technology, to adopt comparatively general method in recent years, has the features such as easy to use, economic, stable.
In absorption method, conventional sorbing material has active carbon, bone carbon (calcium hydroxy phosphate) and activated alumina etc. at present.Wherein active carbon has larger specific area, but its aperture is also larger, and fluorine ion enters behind hole, is difficult to be adsorbed in the hole of active carbon.Therefore active carbon is very low to fluorine ion adsorbance, and can not regenerate, adsorb saturated after, can only abandon, operating cost is quite high.Calcium hydroxy phosphate has certain adsorption effect to fluorine, but also Shortcomings: the one, material price is high; The 2nd, intensity difference, easily broken; The 3rd, running is complicated, and management difficulty is very high, and while especially regenerating, regenerated liquid concentration is controlled bad, can cause material fragmentation to lose efficacy, and these shortcomings are restricted its application.Activated alumina is current a kind of defluorinating agent with the most use in the world, China has the fluorine removal device of 50% left and right to adopt activated alumina, but through facts have proved for many years, also there is following several deficiency in this method, the one, continuous operating time is short, be easy to occur false tired, move and after 4～6 hours, will be interrupted the same time and set up; The 2nd, the recovery time is long, and regeneration is complicated, complex management.As regenerated with aluminum sulfate, the recovery time needs more than 24 hours; As with NaOH regeneration, although time shorten needs to use hydrochloric acid neutralization, in addition, because aluminium is dissolved in acid, slightly do not notice that aluminium is just dissolved by acid and enters in water.Therefore management expectancy is very high, and technique is various, not easy to operate; The 3rd, filtrate is prone to the phenomenon that hardens, and makes water distribution and catchments inhomogeneously, has a strong impact on service life, particularly use after a period of time, filtrate hardens substantially in process tank, not only entirely ineffective, and filtrate and tank body form one cannot be separated, cause tank body to scrap.The 4th, after each regeneration, adsorption capacity all can decline, and causes its service life short, is generally no more than 1 year, and overall use cost is high.Therefore the material for water treatment that exploitation has good adsorption ability to fluorine ion is significant.
Nano material because its yardstick is little, the advantage such as large, the high adsorption capacity of specific area is in widespread attention in fluorinated water is processed.Yet in actual applications,, because mostly nano material is fine-powder, in the time of in being put into water, these fine particles are easy to reunite and inactivation, thereby cause absorption property to decline.And, thereby after water treatment, need Separation of Solid and Liquid to increase cost.In addition, in actual use, pure nano material is difficult to reclaim and recycling, once recovery is not thorough, by causing the nano material of having adsorbed fluorine to be retained in water, causes secondary pollution.
Summary of the invention
For solving problems of the prior art, the object of the present invention is to provide a kind of preparation method of natural minerals loaded nano defluorinating agent, effectively improve the adsorption capacity to fluorine in water, avoided the problem of nano material reunion inactivation and secondary pollution water body simultaneously.
The technical solution adopted in the present invention:
A preparation method for natural minerals loaded nano defluorinating agent, comprises the following steps:
(1) high-temperature activation is processed: the natural zeolite that is 1-3mm by particle diameter carries out high-temperature process;
(2) acid activation is processed: the zeolite after high-temperature activation is processed is that 1:1-2.5 kg/L joins in acid solution and carries out acid activation processing by mass volume ratio, then wash to pH value be 6-7, refilter, be dried;
(3) alkali activation processing: be that 1:1-2.5 kg/L joins and carries out alkali activation processing in aqueous slkali by mass volume ratio by zeolite dry in (2); Then wash to pH value as 7-8, refilter, dry;
(4) reacting metal salt: be that 1:1-3 kg/L joins and reacts 12-48 hour in metal salt solution by mass volume ratio by zeolite dry in (3); Then after adjusting pH to be 5-6, then through washing, filter, dry and to obtain natural minerals loaded nano defluorinating agent.
Further, the temperature of high-temperature process is that 400-1000 ℃, time are 3-20 hour in described step (1).
Further, acid solution is that in sulfuric acid or hydrochloric acid, at least one is dissolved in the acid solution that the concentration that forms in deionized water is 2-15% in described step (2); The described acid activation processing time is 6-48 hour.
Further, aqueous slkali is that at least one in NaOH, potassium hydroxide or ammoniacal liquor is dissolved in the aqueous slkali that the concentration that forms in deionized water is 2-18% in described step (3); The described alkali activation processing time is 6-48 hour.
Further, in described step (4), in metal salt solution, the concentration of metal ion is 0.3-5mol/L; Described metal ion is the salt-mixture of aluminium salt, aluminium salt and molysite or the salt-mixture of aluminium salt and magnesium salts;
Further, described aluminium salt is at least one in aluminum nitrate, aluminum sulfate, oxalic acid aluminium, aluminium acetate or aluminium chloride;
Described molysite is at least one in ferric nitrate, ferric sulfate, ferric oxalate, ferric acetate or iron chloride;
Described magnesium salts is at least one in magnesium nitrate, magnesium sulfate, magnesium oxalate, magnesium acetate or magnesium chloride.
The temperature of further, drying in described step (4) is that 125-195 ℃, time are 1-10 hour.
So a kind of natural minerals loaded nano defluorinating agent of the present invention is that employing natural zeolite is carrier, by carrier is carried out to high-temperature activation processing, after acid activation, cleaning, filtration, dry, alkali activates, clean, filter, be dried etc. processed, again zeolite is added to metal salt solution, by technological processes such as solution reaction, cleaning, filtration, oven dry reactions, prepare.
Because the crystal structure of zeolite is to be linked to be three-dimensional screen work by silicon (aluminium) oxygen tetrahedron, in screen work, there are hole of all sizes and passage, there is very large opening.The molecule of other materials that vary in size can be drawn or be filtered to these holes and passage.Zeolite is because long-term existence is in occurring in nature, duct can be occupied by some organic matters and inorganic matter, utilize zeolite as nano material carrier before, need to carry out pretreatment to remove organic matter and the inorganic matter impurity in duct to zeolite, thereby the hole in zeolite and passage are discharged fully, so that nano material can fully enter.In the present invention, first utilize high-temperature process to remove the organic impurities in zeolite cavity, then remove the inorganic matter impurity in zeolite cavity by acid treatment and alkali treatment.When zeolite adds in metal salt solution, metal ion is due to the diffusion of self, and its concentration of various piece in solution is essentially identical.In addition, the diameter due to metal ion is 10
-10meter level, its size is less than the hole of zeolite and passage, so metal ion is easy to enter in the hole and passage of zeolite, and because electrostatic attraction effect is adsorbed in the hole and passage of zeolite, then first by adding OH
-reaction generates Z-M(OH) x(wherein Z be zeolitic frameworks, M is metal ion), then generate Z-MO by the thermal response that is subject under certain high temperature
(x-1)/2oH, concrete reaction is as follows:
Z—M
x++xOH
-?→?Z—M（OH）x
Z-M(OH) x (being subject to thermal response) → Z-MO
(x-1)/2oH+ (x-1)/2H
2o
Wherein Z is zeolitic frameworks, and M is metal ion
Hole and channel interior reaction at zeolite have generated nano adsorption material, become natural minerals loaded nano defluorinating agent.
When water is processed, packed in Filter column or filter core, the fluorine ion in the nano material adsorbed water in zeolite cavity, and be together fixed in zeolite cavity, avoid water body to cause secondary pollution; After its Adsorption of fluoride reaches capacity, can utilize the alum solution of concentration 2%-5% to regenerate to this natural minerals loaded nano defluorinating agent, then water can be repeatedly used after rinsing well, has adsorbed the nano material of fluorine without recovery, has greatly reduced the cost of defluorination.
So the present invention has following beneficial effect:
(1) because natural zeolite has stronger mechanical strength, its inside has been full of trickle hole and passage, still can effectively nano material be fixed in its inner duct, thereby avoid nano material to run off under the condition of current.
(2) many holes of zeolite and passage can effectively prevent the reunion of nano material, can avoid causing because nano material is reunited the decline of defluorinating agent self absorption property.
(3) because zeolite is loose structure, there is the performances such as certain absorption, ion-exchange, therefore the organic micro-pollutants such as the inorganic micropollutants such as heavy metal ion of zeolite in also can absorbed portion water and humic acid in nano material Adsorption of fluoride, has the function of further purifying waste water.
(4) in defluorinating agent, after the fluorine in nano material adsorbed water, be fixed in the hole and passage of zeolite, thereby avoid it to stay in water body and water body is caused to secondary pollution.
(5) in use, defluorinating agent of the present invention is packed in Filter column or filter core, after its Adsorption of fluoride reaches capacity, after utilizing the alum solution of concentration 2%-5% to regenerate, water can be repeatedly used after rinsing well, the nano material of having adsorbed fluorine without recovery, has greatly reduced the cost of defluorination.
(6) defluorinating agent provided by the invention has Large ratio surface, can provide more avtive spot to realize fluorine high-adsorption-capacity, can be widely used in the aspects such as high fluorine surface water, ground water cleaning processing and fluorine containing waste water processing.
(7) defluorinating agent of the present invention is to be prepared under normal pressure, and technique is simple, and equipment investment is few, and processing ease is easy to realize extensive preparation.
accompanying drawing explanation:
Fig. 1 is the scanning electron microscope (SEM) photograph of the natural minerals loaded nano defluorinating agent prepared of the present invention;
Fig. 2 is that defluorinating agent and activated alumina prepared by the present invention removes fluorine test effect comparison diagram;
Fig. 3 is that defluorinating agent prepared by the present invention is placed in Filter column and carries out the last fluorine concentration of dynamic defluorination experiment rear solution with the variation diagram of processing the water yield.
the specific embodiment:
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment mono-:
(1) high-temperature activation is processed: the natural zeolite that is 1mm by 100g particle diameter is to process 8 hours under the high temperature of 700 ℃ in temperature;
(2) acid activation is processed: it is in 7% hydrochloric acid solution, to carry out acid activation to process 20 hours that the zeolite after high-temperature activation is processed joins 200ml concentration, then wash to pH value be 6.5, refilter, be dried;
(3) alkali activation processing: it is to carry out alkali activation processing 24 hours in 10% sodium hydroxide solution that zeolite dry in (2) is joined to 200ml concentration; Then wash to pH value be 7.5, refilter, dry;
(4) reacting metal salt: zeolite dry in (3) is joined in the liquor alumini chloridi that 150ml concentration is 4mol/L and reacted 18 hours; Then after adjusting pH to be 5.5, then through washing, filter, dry 4.5 hours in 155 ℃, obtain natural minerals loaded nano defluorinating agent.
The scanning electron microscope (SEM) photograph of natural minerals loaded nano defluorinating agent prepared by the present embodiment as shown in Figure 1.
Natural minerals loaded nano defluorinating agent prepared by the present embodiment and activated alumina are to the fluoride ion removing Contrast on effect of variable concentrations as shown in Figure 2, wherein abscissa is the concentration of fluorine in pending fluorine solution, and ordinate is the clearance of defluorinating agent to fluorine in variable concentrations fluorine solution.Pending fluorine-containing liquor capacity is 100ml, and having selected respectively fluorinion concentration is that 0.2ppm, 0.5ppm, 1ppm, 2ppm, 5ppm, 10ppm and 20ppm are as experimental subjects.Test nanophase defluoridation agent used and the amount of activated alumina and be 1g.As can be seen from Figure 2 the prepared natural minerals loaded nano defluorinating agent of the present invention reaches 81-95% to the removal effect of fluorine, and activated alumina is only 30-75% to the removal effect of fluorine.
The natural minerals loaded nano defluorinating agent of embodiment one preparation to be placed in to Filter column carry out the last fluorine concentration of the rear water of dynamic defluorination experiment with the variation relation figure that processes the water yield as shown in Figure 3.Wherein in the pending aqueous solution, the concentration of fluorine is 10ppm, and pH value is 7, flow velocity 2L/h; In Filter column, the volume of filtrate is 1 liter.In Fig. 3, abscissa represents the ratio of filtrate volume in the volume of handled water and Filter column, and ordinate represents to process the content of fluorine in rear water, and unit is ppm.Two dotted lines that are arranged in 1ppm and 1.2ppm in figure are respectively the values of national < < drinking water sanitary standard > > (GB5749-2006) defined city and country drinking water fluorine content.
As can be seen from Figure 3 the natural minerals loaded nano defluorinating agent of unit volume can be processed the water (initial fluorine concentration 10ppm) of 205 times of himself volumes, makes the content of fluorine in water lower than 1ppm; After having processed 222 times of water of defluoridation filter material volume, fluorine content after processing in water is 1.2ppm, and it all meets the numerical value of < < drinking water sanitary standard > > (GB5749-2006).So natural minerals loaded nano defluorinating agent prepared by the present invention can effectively be removed fluorine that fluorine exceeds standard in water to national standard.
Embodiment bis-:
(1) high-temperature activation is processed: the natural zeolite that is 1.5mm by 100g particle diameter is to process 20 hours under the high temperature of 400 ℃ in temperature;
(2) acid activation is processed: it is in 2% hydrochloric acid solution, to carry out acid activation to process 48 hours that the zeolite after high-temperature activation is processed joins 250ml concentration, then wash to pH value be 6, refilter, be dried;
(3) alkali activation processing: it is to carry out alkali activation processing 12 hours in 15% sodium hydroxide solution that zeolite dry in (2) is joined to 150ml concentration; Then wash to pH value be 7, refilter, dry;
(4) reacting metal salt: zeolite dry in (3) is joined in the aluminum sulfate solution that 350ml concentration is 0.3mol/L and reacted 48 hours; Then after adjusting pH to be 6, then through washing, filter, dry 1 hour in 195 ℃, obtain natural minerals loaded nano defluorinating agent.
Embodiment tri-:
(1) high-temperature activation is processed: the natural zeolite that is 3mm by 100g particle diameter is to process 3 hours under the high temperature of 1000 ℃ in temperature;
(2) acid activation is processed: it is in 15% sulfuric acid solution, to carry out acid activation to process 6 hours that the zeolite after high-temperature activation is processed joins 100ml concentration, then wash to pH value be 6.2, refilter, be dried;
(3) alkali activation processing: it is to carry out alkali activation processing 12 hours in 18% potassium hydroxide solution that zeolite dry in (2) is joined to 100ml concentration; Then wash to pH value be 7, refilter, dry;
(4) reacting metal salt: zeolite dry in (3) is joined in the aluminum nitrate solution that 105ml concentration is 5mol/L and reacted 12 hours; Then after adjusting pH to be 6, then through washing, filter, dry 10 hours in 125 ℃, obtain natural minerals loaded nano defluorinating agent.
Embodiment tetra-:
(1) high-temperature activation is processed: the natural zeolite that is 1mm by 100g particle diameter is to process 5 hours under the high temperature of 800 ℃ in temperature;
(2) acid activation is processed: it is in 10% sulfuric acid solution, to carry out acid activation to process 16 hours that the zeolite after high-temperature activation is processed joins 150ml concentration, then wash to pH value be 7, refilter, be dried;
(3) alkali activation processing: it is to carry out alkali activation processing 6 hours in 18% ammonia spirit that zeolite dry in (2) is joined to 100ml concentration; Then wash to pH value be 8, refilter, dry;
(4) reacting metal salt: zeolite dry in (3) is joined in the solution that 200ml is comprised of 0.3mol aluminium chloride, 0.15mol ferric nitrate and reacted 30 hours; Then after adjusting pH to be 6, then through washing, filter, dry 6 hours in 145 ℃, obtain natural minerals loaded nano defluorinating agent.
Embodiment five:
(1) high-temperature activation is processed: the natural zeolite that is 2.5mm by 100g particle diameter is to process 12 hours under the high temperature of 600 ℃ in temperature;
(2) acid activation is processed: it is in 12% hydrochloric acid solution, to carry out acid activation to process 15 hours that the zeolite after high-temperature activation is processed joins 150ml concentration, then wash to pH value be 6.7, refilter, be dried;
(3) alkali activation processing: it is to carry out alkali activation processing 48 hours in 2% sodium hydroxide solution that zeolite dry in (2) is joined to 250ml concentration, then wash to pH value be 7.8, refilter, dry;
(4) reacting metal salt: zeolite dry in (3) is joined in the solution being formed by 0.1mol aluminum sulfate, 0.1mol ferric acetate and 250ml water and reacted 24 hours; Then after adjusting pH to be 6, then through washing, filter, dry 6.5 hours in 140 ℃, obtain natural minerals loaded nano defluorinating agent.
Embodiment six:
(1) high-temperature activation is processed: the natural zeolite that is 1.5mm by 100g particle diameter is to process 14 hours under the high temperature of 500 ℃ in temperature;
(2) acid activation is processed: it is in 5% hydrochloric acid solution, to carry out acid activation to process 30 hours that the zeolite after high-temperature activation is processed joins 200ml concentration, then wash to pH value be 6, refilter, be dried;
(3) alkali activation processing: it is to carry out alkali activation processing 36 hours in 5% sodium hydroxide solution that zeolite dry in (2) is joined to 200ml concentration; Then wash to pH value be 7.5, refilter, dry;
(4) reacting metal salt: zeolite dry in (3) is joined in the solution being formed by 0.25mol aluminum nitrate, 0.2mol magnesium chloride and 150ml water to 24 hours reaction time; Then after adjusting pH to be 6, then through washing, filter, dry 2 hours in 170 ℃, obtain natural minerals loaded nano defluorinating agent.
Embodiment seven:
(1) high-temperature activation is processed: the natural zeolite that is 2mm by 100g particle diameter is to process 10 hours under the high temperature of 650 ℃ in temperature;
(2) acid activation is processed: it is in 11% sulfuric acid solution, to carry out acid activation to process 14 hours that the zeolite after high-temperature activation is processed joins 150ml concentration, then wash to pH value be 6.7, refilter, be dried;
(3) alkali activation processing: it is to carry out alkali activation processing 24 hours in 10% potassium hydroxide solution that zeolite dry in (2) is joined to 150ml concentration; Then wash to pH value be 7.5, refilter, dry;
(4) reacting metal salt: zeolite dry in (3) is joined in the solution being formed by 0.1mol aluminum nitrate, 0.05mol magnesium nitrate and 300ml water to 24 hours reaction time; Then after adjusting pH to be 6, then through washing, filter, dry 3.5 hours in 160 ℃, obtain natural minerals loaded nano defluorinating agent.
Above embodiment is not limited only to protection scope of the present invention, all based on basic thought of the present invention and all belonging in protection scope of the present invention of modifying or change.
Claims (7)
1. a preparation method for natural minerals loaded nano defluorinating agent, is characterized in that: comprise the following steps:
(1) high-temperature activation is processed: the natural zeolite that is 1-3mm by particle diameter carries out high-temperature process;
(2) acid activation is processed: the zeolite after high-temperature activation is processed is that 1:1-2.5 kg/L joins in acid solution and carries out acid activation processing by mass volume ratio, then wash to pH value be 6-7, refilter, be dried;
(3) alkali activation processing: be that 1:1-2.5 kg/L joins and carries out alkali activation processing in aqueous slkali by mass volume ratio by zeolite dry in (2); Then wash to pH value as 7-8, refilter, dry;
(4) reacting metal salt: be that 1:1-3 kg/L joins and reacts 12-48 hour in metal salt solution by mass volume ratio by zeolite dry in (3); Then after adjusting pH to be 5-6, then through washing, filter, dry and to obtain natural minerals loaded nano defluorinating agent.
2. preparation method according to claim 1, is characterized in that: in described step (1), the temperature of high-temperature process is that 400-1000 ℃, time are 3-20 hour.
3. preparation method according to claim 1, is characterized in that: in described step (2), acid solution is that in sulfuric acid or hydrochloric acid, at least one is dissolved in the acid solution that the concentration that forms in deionized water is 2-15%; The described acid activation processing time is 6-48 hour.
4. preparation method according to claim 1, is characterized in that: in described step (3), aqueous slkali is that at least one in NaOH, potassium hydroxide or ammoniacal liquor is dissolved in the aqueous slkali that the concentration that forms in deionized water is 2-18%; The described alkali activation processing time is 6-48 hour.
5. preparation method according to claim 1, is characterized in that: in described step (4), in metal salt solution, the concentration of metal ion is 0.3-5mol/L; Described metal ion is the salt-mixture of aluminium salt, aluminium salt and molysite or the salt-mixture of aluminium salt and magnesium salts.
6. preparation method according to claim 5, is characterized in that: described aluminium salt is at least one in aluminum nitrate, aluminum sulfate, oxalic acid aluminium, aluminium acetate or aluminium chloride;
Described molysite is at least one in ferric nitrate, ferric sulfate, ferric oxalate, ferric acetate or iron chloride;
Described magnesium salts is at least one in magnesium nitrate, magnesium sulfate, magnesium oxalate, magnesium acetate or magnesium chloride.
7. preparation method according to claim 1, is characterized in that: the temperature of drying in described step (4) is that 125-195 ℃, time are 1-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310723159.1A CN103706326B (en) | 2013-12-25 | 2013-12-25 | A kind of preparation method of natural minerals loaded nano defluorinating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310723159.1A CN103706326B (en) | 2013-12-25 | 2013-12-25 | A kind of preparation method of natural minerals loaded nano defluorinating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103706326A true CN103706326A (en) | 2014-04-09 |
| CN103706326B CN103706326B (en) | 2016-07-20 |
Family
ID=50399886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310723159.1A Active CN103706326B (en) | 2013-12-25 | 2013-12-25 | A kind of preparation method of natural minerals loaded nano defluorinating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103706326B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923721A (en) * | 2014-05-08 | 2014-07-16 | 重庆大学 | Fluoride solidifying agent for treating fluorine pollution caused by burning coal and preparation method and application method thereof |
| CN106865655A (en) * | 2017-04-12 | 2017-06-20 | 明光市国星凹土有限公司 | A kind of attapulgite sewage-treating agent and preparation method thereof |
| CN106943989A (en) * | 2017-04-12 | 2017-07-14 | 明光市国星凹土有限公司 | It is a kind of to be used for attapulgite modified soda acid combined techniques |
| CN108940235A (en) * | 2018-07-25 | 2018-12-07 | 广西大学 | The in-situ precipitate preparation method and application of geo-polymer defluorinating agent |
| CN110801806A (en) * | 2019-11-20 | 2020-02-18 | 苏州麦王环境科技有限公司 | Composite defluorination filter material and preparation method thereof |
| RU2733391C1 (en) * | 2020-04-19 | 2020-10-01 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр «Институт общей физики им. А.М. Прохорова Российской академии наук» (ИОФ РАН) | Method of measuring refractive indices of optical materials in solid state or in form of melt |
| CN113003751A (en) * | 2021-04-19 | 2021-06-22 | 中国建筑设计研究院有限公司 | Underground water purification method and system |
| CN113735236A (en) * | 2021-09-29 | 2021-12-03 | 东北大学 | Preparation of defluorinating agent and treatment method of fluorine-containing waste liquid |
| CN117463305A (en) * | 2023-12-27 | 2024-01-30 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
| CN117619352A (en) * | 2024-01-26 | 2024-03-01 | 中国科学院合肥物质科学研究院 | Degradation agent of perfluoro compound and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393401A (en) * | 2001-07-04 | 2003-01-29 | 北京运衡兴源科技发展有限公司 | Modified zeolite and its preparing process, application and regeneration |
| CN101406823A (en) * | 2007-10-10 | 2009-04-15 | 宜兴市得力耐磨炉料有限公司 | Method for producing high-efficient defluorination active micropore ceramic stuffing |
-
2013
- 2013-12-25 CN CN201310723159.1A patent/CN103706326B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393401A (en) * | 2001-07-04 | 2003-01-29 | 北京运衡兴源科技发展有限公司 | Modified zeolite and its preparing process, application and regeneration |
| CN101406823A (en) * | 2007-10-10 | 2009-04-15 | 宜兴市得力耐磨炉料有限公司 | Method for producing high-efficient defluorination active micropore ceramic stuffing |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923721A (en) * | 2014-05-08 | 2014-07-16 | 重庆大学 | Fluoride solidifying agent for treating fluorine pollution caused by burning coal and preparation method and application method thereof |
| CN103923721B (en) * | 2014-05-08 | 2015-07-15 | 重庆大学 | Fluoride solidifying agent for treating fluorine pollution caused by burning coal and preparation method and application method thereof |
| CN106865655A (en) * | 2017-04-12 | 2017-06-20 | 明光市国星凹土有限公司 | A kind of attapulgite sewage-treating agent and preparation method thereof |
| CN106943989A (en) * | 2017-04-12 | 2017-07-14 | 明光市国星凹土有限公司 | It is a kind of to be used for attapulgite modified soda acid combined techniques |
| CN108940235A (en) * | 2018-07-25 | 2018-12-07 | 广西大学 | The in-situ precipitate preparation method and application of geo-polymer defluorinating agent |
| CN110801806A (en) * | 2019-11-20 | 2020-02-18 | 苏州麦王环境科技有限公司 | Composite defluorination filter material and preparation method thereof |
| RU2733391C1 (en) * | 2020-04-19 | 2020-10-01 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр «Институт общей физики им. А.М. Прохорова Российской академии наук» (ИОФ РАН) | Method of measuring refractive indices of optical materials in solid state or in form of melt |
| CN113003751A (en) * | 2021-04-19 | 2021-06-22 | 中国建筑设计研究院有限公司 | Underground water purification method and system |
| CN113735236A (en) * | 2021-09-29 | 2021-12-03 | 东北大学 | Preparation of defluorinating agent and treatment method of fluorine-containing waste liquid |
| CN117463305A (en) * | 2023-12-27 | 2024-01-30 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
| CN117463305B (en) * | 2023-12-27 | 2024-04-02 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
| CN117619352A (en) * | 2024-01-26 | 2024-03-01 | 中国科学院合肥物质科学研究院 | Degradation agent of perfluoro compound and application thereof |
| CN117619352B (en) * | 2024-01-26 | 2024-04-09 | 中国科学院合肥物质科学研究院 | Degradation agent of perfluoro compound and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103706326B (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103706326B (en) | A kind of preparation method of natural minerals loaded nano defluorinating agent | |
| CN101007261B (en) | Zeolite adsorbent and its preparation method | |
| CN101805037B (en) | Method for removing humic acid pollutants in water by magnetic chitosan particle | |
| Tang et al. | Highly efficient adsorption of uranium (VI) from aqueous solution by a novel adsorbent: titanium phosphate nanotubes | |
| CN101973620A (en) | Method for removing heavy metal ions in water by using graphene oxide sheet | |
| CN112337427B (en) | La @ Zr @ SiO2Preparation method of @ bentonite composite phosphorus removal adsorbent | |
| CN103464094A (en) | Preparation method of nano-iron modified zeolite | |
| CN109012565A (en) | A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating | |
| CN111167402B (en) | Zinc-cobalt Prussian blue analogue adsorbent with hollow structure and preparation method and application thereof | |
| CN102268114A (en) | Defluorinating resin with compound functions and preparation method thereof | |
| CN103253788B (en) | Method for removing fluorides in water through aluminum base composite metal oxide-based fluorine removing absorption material complexation-absorption | |
| CN103204562B (en) | Method for removing antibiotic contamination by adsorption of copper sulphide | |
| CN107252674A (en) | A kind of dephosphorization agent based on ferronickel binary hydrotalcite | |
| Zou et al. | Adsorption research of tetracycline from water by HCl-modified zeolite | |
| CN104016434A (en) | Method for purifying sewage containing heavy metal by utilizing calcium metasilicate and recycling heavy metal | |
| Wang et al. | Three-dimensional graphene/La (OH) 3-nanorod aerogel adsorbent by self-assembly process for enhanced removal and recovery of phosphate in wastewater | |
| Tee et al. | Lanthanum carbonate nanoparticles confined within anion exchange resin for phosphate removal from river water: Batch and fixed-bed column study | |
| Li et al. | High-efficient phosphate removal from wastewater by weak magnetic La (OH) 3 modified platanus biochar | |
| CN111632579A (en) | Defluorination resin and preparation method thereof | |
| CN109317110A (en) | A kind of application for preparing and its going copper ion in water removal of sodium alginate/smectite composite gel material | |
| CN101088604A (en) | Process of preparing filter material for reducing fluoride content and improving water quality | |
| CN103578594B (en) | A kind of use nanometer Fe3O4-CeO2The method of radionuclide removed by material | |
| Wang et al. | Synchronously construction of hierarchical porous channels and cationic surface charge on lanthanum-hydrogel for rapid phosphorus removal | |
| CN110064378B (en) | Magnetic chitosan carbon sphere with high adsorption performance and preparation method and application thereof | |
| CN103894139B (en) | The preparation method of loaded stratiform hydroxyl oxidize magnesium base composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |