CN103706326B - A kind of preparation method of natural minerals loaded nano defluorinating agent - Google Patents
A kind of preparation method of natural minerals loaded nano defluorinating agent Download PDFInfo
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Abstract
The preparation method of a kind of natural minerals loaded nano defluorinating agent of disclosure, its method includes high-temperature activation process, acid activation process, alkali activation processing and reacting metal salt.Owing to natural zeolite has stronger mechanical strength, trickle hole and passage it is filled with inside it, utilize it as the carrier of nanophase defluoridation material, still can effectively by fixing for nano material duct therein when current, thus avoiding reunion and the loss of nano material, improve the ability of its Adsorption of fluoride and renewable recycling, reduce the cost of fluorine removal.The defluorinating agent of the present invention has bigger specific surface area, using the teaching of the invention it is possible to provide more avtive spot realizes fluorine high-adsorption-capacity, can be widely applied to the aspects such as high fluorine surface water, ground water cleaning process and fluorine containing waste water process.
Description
Background technology
Fluorine is one of trace element necessary to human body, but take the photograph human body day fluorine amount excessive time, endemic fluorosis will be caused.Long-term drink high-fluorine water, will cause fluorosis, cause dental fluorosis and osteofluorosis, gently then cause tooth to go bad, come off, heavy then cause osteosclerosis or osteoporosis, even paralyse, cause people's disability.Investigation according to Ministry of Public Health shows, endemic fluorosis is extremely wide in China's distribution, and overwhelming majority province has endemic fluorosis to exist.Therefore, effectively control and the fluorine removed in water body are the important topics being related to environment and human health.
China's endemic fluorosis is broadly divided into three kinds: one is Water fluorosis, and this is a kind of type that endemic area distribution is the widest, number of patients is maximum, is distributed mainly on the wide geographic area to the north of Kun Lun Mountain, the Qinling Mountains, Huaihe River.The second is Coal burn induced fluorosis, is distributed mainly on southern each provinces and regions 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.Water fluorosis accounts for very big ratio as can be seen here, and the distribution of fluorosis and hazardness are all very big.Currently mainly reducing fluoride method has ion exchange, absorption method, electroosmose process and hyperfiltration etc..Wherein absorption method is to adopt comparatively general method in water treatment technology in recent years, has the features such as easy to use, economic, stable.
Adsorbing material conventional at present in absorption method has activated carbon, bone carbon (calcium hydroxy phosphate) and activated alumina etc..Wherein activated carbon has bigger specific surface area, but its aperture is also relatively larger, and fluorion is difficult to be adsorbed in the hole of activated carbon after entering hole.Therefore activated carbon is non-normally low to fluorion adsorbance, and can not regenerate, adsorb saturated after, can only abandon, operating cost is at a relatively high.Fluorine is had certain adsorption effect by calcium hydroxy phosphate, but there is also deficiency: one is that material price is high；Two is intensity difference, broken；Three is operating complexity, and management difficulty is very high, and when especially regenerating, regeneration solution concentration controls bad, and material fragmentation can be caused to lose efficacy, and these shortcomings make it apply to be restricted.Activated alumina is a kind of defluorinating agent with the most use in the world at present, China has the fluorine removal device of about 50% to adopt activated alumina, but facts have proved through for many years, this method there is also following several deficiency, one is that continuous operating time is short, being easy to occur false tired, to be interrupted the same time after running 4～6 hours sets up；Two is that the recovery time is long, regeneration complexity, complex management.As regenerated with aluminum sulfate, the recovery time needs more than 24 hours；As regenerated with sodium hydroxide, although the time shortens, but hydrochloric acid need to be used to neutralize, further, since aluminum is dissolved in acid, slightly do not notice that aluminum is just entered in water by acid-soluble solution.Therefore management requires very high, and process-intensive not easily operates；Three is that filtrate the phenomenon that hardens easily occurs, and makes water distribution and catchments uneven, has a strong impact on service life, and after a period of time, filtrate hardens substantially in process tank, not only complete failure, and filtrate and tank body form one cannot separate, and causes tank body to scrap.Four is that after regeneration every time, adsorption capacity all can decline, and causes that its service life is short, is usually no more than 1 year, and overall use cost is high.Therefore the material for water treatment that fluorion is had good adsorption ability is developed significant.
Nano material is in widespread attention in Ca reservoir because of advantages such as its yardstick is little, specific surface area big, high adsorption capacities.But in actual applications, owing to mostly nano material is fine-powder, when being put in water, these fine particles are easy to reunite and inactivate, thus causing that absorption property declines.Further, water needs solid-liquid separation thus increasing cost after processing.Additionally, in actual use, pure nano material is difficult to reclaim and reuse, once reclaim not thorough, by causing that the nano material having adsorbed fluorine is retained in water, causes secondary pollution.
Summary of the invention
For solving problems of the prior art, the preparation method that it is an object of the invention to provide a kind of natural minerals loaded nano defluorinating agent, it is effectively improved the absorbability of fluorine in water, the problem avoiding nano material reunion inactivation and secondary pollution water body simultaneously.
The technical solution adopted in the present invention:
The preparation method of a kind of natural minerals loaded nano defluorinating agent, comprises the following steps:
(1) high-temperature activation processes: the natural zeolite that particle diameter is 1-3mm is carried out high-temperature process；
(2) acid activation processes: the zeolite after being processed by high-temperature activation is that 1:1-2.5kg/L joins and carries out acid activation process in acid solution by mass volume ratio, and being washed out to pH value is 6-7, refilters, dry；
(3) alkali activation processing: be that 1:1-2.5kg/L joins and carries out alkali activation processing in aqueous slkali by mass volume ratio by zeolite dry in (2)；Being washed out to pH value is 7-8, refilters, dries；
(4) reacting metal salt: be that 1:1-3kg/L joins in metal salt solution and reacts 12-48 hour by mass volume ratio by zeolite dry in (3)；Then adjusting solution ph is after 5-6, then through washing, filter, dry and to obtain natural minerals loaded nano defluorinating agent.
Further, in described step (1) temperature of high-temperature process be 400-1000 DEG C, the time be 3-20 hour.
Further, in described step (2) acid solution be in sulphuric acid or hydrochloric acid at least one be dissolved in deionized water formed the acid solution that concentration is 2-15%；The described acid activation process time is 6-48 hour.
Further, in described step (3), aqueous slkali is the aqueous slkali that concentration is 2-18% that at least one in sodium hydroxide, potassium hydroxide or ammonia is dissolved in deionized water to be formed；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 the salt-mixture of aluminium salt, aluminium salt and iron salt or aluminium salt and magnesium salt；
Further, described aluminium salt is at least one in aluminum nitrate, aluminum sulfate, oxalic acid aluminum, aluminium acetate or aluminum chloride；
Described iron salt is at least one in ferric nitrate, iron sulfate, ferric oxalate, ferric acetate or iron chloride；
Described magnesium salt is at least one in magnesium nitrate, magnesium sulfate, magnesium oxalate, magnesium acetate or magnesium chloride.
Further, the temperature dried in described step (4) is 125-195 DEG C, the time is 1-10 hour.
So a kind of natural minerals loaded nano defluorinating agent of the present invention is employing natural zeolite is carrier, by carrier is carried out high-temperature activation process, acid activation, cleaning, filtration, dry, alkali activation, clean, filter, dry etc. process after, again zeolite is added metal salt solution, prepared by technological processes such as solution reaction, cleaning, filtration, drying reactions.
Owing to the crystal structure of zeolite is the screen work being linked to be three-dimensional by silicon (aluminum) oxygen tetrahedron, screen work has hole of all sizes and passage, there is very big opening.These holes and passage can be drawn or filter the molecule of other materials varied in size.Zeolite is owing to long-term existence is in nature, duct can occupied by some Organic substances and inorganic matter, before utilizing zeolite as nano material carrier, need zeolite to carry out pretreatment with the Organic substance removing in duct and inorganic contaminants, thus the hole in zeolite and passage are discharged fully, in order to nano material can be well into.The present invention removes the organic impurities in zeolite cavity first with high-temperature process, processes, again through acid treatment and alkali, the inorganic contaminants removed in zeolite cavity.When zeolite adds in metal salt solution, metal ion is due to the diffusion of self, and the concentration of its various piece in the solution is essentially identical.Additionally, due to the diameter of metal ion is 10-10Meter level, it is sized to less than the hole of zeolite and passage, and therefore metal ion easily enters in hole and the passage of zeolite, and is adsorbed in hole and the passage of zeolite due to electrostatic attraction effect, then first passes through addition OH-Reaction generates Z M(OH) x(wherein Z is zeolitic frameworks, M is metal ion), again through being generated Z MO by thermal response under certain high temperature(x-1)/2OH, concrete reaction is as follows:
Z—Mx++xOH-→ Z M(OH) x
Z M(OH) x(is by thermal response) → Z MO(x-1)/2OH+(x-1)/2H2O
Wherein Z is zeolitic frameworks, and M is metal ion
React in the hole of zeolite and channel interior and generate nano adsorption material, become natural minerals loaded nano defluorinating agent.
When water is processed, it is loaded in Filter column or filter element, the fluorion in nano material absorption water in zeolite cavity, and be together fixed in zeolite cavity, it is to avoid water body is caused secondary pollution；After its Adsorption of fluoride reaches capacity, this natural minerals loaded nano defluorinating agent is regenerated by the alum solution of available concentration 2%-5%, then can repeatedly use after rinsing well with water, it is not necessary to reclaim the nano material having adsorbed fluorine, significantly reduce the cost of fluorine removal.
So the method have the advantages that
(1) owing to natural zeolite has stronger mechanical strength, inside it, being filled with trickle hole and passage, still can effectively nano material being fixed in duct therein when current, thus avoiding nano material to run off.
(2) a plurality of hole of zeolite and passage can effectively prevent the reunion of nano material, it is possible to avoid causing the decline of defluorinating agent self absorption property because nano material is reunited.
(3) owing to zeolite is loose structure, there is the performances such as certain absorption, ion exchange, therefore while nano material Adsorption of fluoride zeolite also can the organic micro-pollutants such as inorganic micropollutants and humic acids such as heavy metal ion in absorbed portion water, there is the function of further scrubbing water.
(4) defluorinating agent is fixed in hole and the passage of zeolite after the fluorine in nano material absorption water, thus avoiding it to stay, in water body, water body to be caused secondary pollution.
(5) in use, the defluorinating agent of the present invention is loaded in Filter column or filter element, after its Adsorption of fluoride reaches capacity, after the alum solution utilizing concentration 2%-5% regenerates, can repeatedly use after rinsing well with water, without reclaiming the nano material having adsorbed fluorine, significantly reduce the cost of fluorine removal.
(6) defluorinating agent provided by the invention has Large ratio surface, using the teaching of the invention it is possible to provide more avtive spot realizes fluorine high-adsorption-capacity, can be widely applied to the aspects such as high fluorine surface water, ground water cleaning process and fluorine containing waste water process.
(7) defluorinating agent of the present invention is to be prepared at ambient pressure, and technique is simple, and equipment investment is few, processing ease, it is easy to accomplish prepare on a large scale.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscope (SEM) photograph of natural minerals loaded nano defluorinating agent prepared by the present invention；
Fig. 2 is that defluorinating agent prepared by the present invention carries out fluorine test effect comparison diagram with activated alumina；
Fig. 3 is that defluorinating agent prepared by the present invention is placed in Filter column and carries out Funing tablet remaining in dynamic fluorine removal experiment rear solution with the variation diagram processing the water yield.
Detailed description of the invention:
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment one:
(1) high-temperature activation processes: carry out the natural zeolite that 100g particle diameter is 1mm under the high temperature that temperature is 700 DEG C processing 8 hours；
(2) acid activation processes: the zeolite after being processed by high-temperature activation joins and carries out acid activation process 20 hours in the hydrochloric acid solution that 200ml concentration is 7%, and being washed out to pH value is 6.5, refilters, dries；
(3) alkali activation processing: zeolite dry in (2) is joined in the sodium hydroxide solution that 200ml concentration is 10% and carries out alkali activation processing 24 hours；Being washed out to pH value is 7.5, refilters, dries；
(4) reacting metal salt: zeolite dry in (3) is joined in the liquor alumini chloridi that 150ml concentration is 4mol/L and reacts 18 hours；Then adjusting solution ph is after 5.5, then through washing, filters, dries 4.5 hours in 155 DEG C, obtains natural minerals loaded nano defluorinating agent.
The scanning electron microscope (SEM) photograph of natural minerals loaded nano defluorinating agent prepared by the present embodiment is 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 vertical coordinate is that defluorinating agent is to the clearance of fluorine in variable concentrations fluorine solution.Pending fluorine-containing liquor capacity is 100ml, and have selected fluorinion concentration respectively is that 0.2ppm, 0.5ppm, 1ppm, 2ppm, 5ppm, 10ppm and 20ppm are as experimental subject.Nanophase defluoridation agent and the amount of activated alumina that experiment is used are 1g.As can be seen from Figure 2 the removal effect of fluorine is reached 81-95% by the natural minerals loaded nano defluorinating agent prepared by the present invention, and the removal effect of fluorine is only 30-75% by activated alumina.
It is that the natural minerals loaded nano defluorinating agent prepared by embodiment one is placed in Filter column to carry out Funing tablet remaining in water after dynamic fluorine removal experiment with the variation relation figure processing the water yield as shown in Figure 3.Wherein in 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 volume and the ratio of filtrate volume in Filter column of handled water, and the content of fluorine in water after vertical coordinate expression process, unit is ppm.Two dotted lines being arranged in 1ppm and 1.2ppm in figure are the value of country " drinking water sanitary standard " (GB5749-2006) defined city and rural potable water Oil repellent respectively.
As can be seen from Figure 3 the natural minerals loaded nano defluorinating agent of unit volume can process the water (initial Funing tablet 10ppm) of himself volume 205 times, makes in water the content of fluorine lower than 1ppm；When, after the 222 times of water having processed defluoridation filter material volume, after process, the Oil repellent 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 remove fluorine that fluorine exceeds standard in water to national standard.
Embodiment two:
(1) high-temperature activation processes: carry out the natural zeolite that 100g particle diameter is 1.5mm under the high temperature that temperature is 400 DEG C processing 20 hours；
(2) acid activation processes: the zeolite after being processed by high-temperature activation joins and carries out acid activation process 48 hours in the hydrochloric acid solution that 250ml concentration is 2%, and being washed out to pH value is 6, refilters, dries；
(3) alkali activation processing: zeolite dry in (2) is joined in the sodium hydroxide solution that 150ml concentration is 15% and carries out alkali activation processing 12 hours；Being washed out to pH value is 7, refilters, dries；
(4) reacting metal salt: zeolite dry in (3) is joined in the aluminum sulfate solution that 350ml concentration is 0.3mol/L and reacts 48 hours；Then adjusting solution ph is after 6, then through washing, filters, dries 1 hour in 195 DEG C, obtains natural minerals loaded nano defluorinating agent.
Embodiment three:
(1) high-temperature activation processes: carry out the natural zeolite that 100g particle diameter is 3mm under the high temperature that temperature is 1000 DEG C processing 3 hours；
(2) acid activation processes: the zeolite after being processed by high-temperature activation joins and carries out acid activation process 6 hours in the sulfuric acid solution that 100ml concentration is 15%, and being washed out to pH value is 6.2, refilters, dries；
(3) alkali activation processing: zeolite dry in (2) is joined in the potassium hydroxide solution that 100ml concentration is 18% and carries out alkali activation processing 12 hours；Being washed out to pH value is 7, refilters, dries；
(4) reacting metal salt: zeolite dry in (3) is joined in the aluminum nitrate solution that 105ml concentration is 5mol/L and reacts 12 hours；Then adjusting solution ph is after 6, then through washing, filters, dries 10 hours in 125 DEG C, obtains natural minerals loaded nano defluorinating agent.
Embodiment four:
(1) high-temperature activation processes: carry out the natural zeolite that 100g particle diameter is 1mm under the high temperature that temperature is 800 DEG C processing 5 hours；
(2) acid activation processes: the zeolite after being processed by high-temperature activation joins and carries out acid activation process 16 hours in the sulfuric acid solution that 150ml concentration is 10%, and being washed out to pH value is 7, refilters, dries；
(3) alkali activation processing: zeolite dry in (2) is joined in the ammonia spirit that 100ml concentration is 18% and carries out alkali activation processing 6 hours；Being washed out to pH value is 8, refilters, dries；
(4) reacting metal salt: zeolite dry in (3) is joined in the 200ml solution being made up of 0.3mol aluminum chloride, 0.15mol ferric nitrate and reacts 30 hours；Then adjusting solution ph is after 6, then through washing, filters, dries 6 hours in 145 DEG C, obtains natural minerals loaded nano defluorinating agent.
Embodiment five:
(1) high-temperature activation processes: carry out the natural zeolite that 100g particle diameter is 2.5mm under the high temperature that temperature is 600 DEG C processing 12 hours；
(2) acid activation processes: the zeolite after being processed by high-temperature activation joins and carries out acid activation process 15 hours in the hydrochloric acid solution that 150ml concentration is 12%, and being washed out to pH value is 6.7, refilters, dries；
(3) alkali activation processing: being joined in the sodium hydroxide solution that 250ml concentration is 2% by zeolite dry in (2) and carry out alkali activation processing 48 hours, being washed out to pH value is 7.8, refilters, dries；
(4) reacting metal salt: zeolite dry in (3) is joined in the solution formed by 0.1mol aluminum sulfate, 0.1mol ferric acetate and 250ml water and reacts 24 hours；Then adjusting solution ph is after 6, then through washing, filters, dries 6.5 hours in 140 DEG C, obtains natural minerals loaded nano defluorinating agent.
Embodiment six:
(1) high-temperature activation processes: carry out the natural zeolite that 100g particle diameter is 1.5mm under the high temperature that temperature is 500 DEG C processing 14 hours；
(2) acid activation processes: the zeolite after being processed by high-temperature activation joins and carries out acid activation process 30 hours in the hydrochloric acid solution that 200ml concentration is 5%, and being washed out to pH value is 6, refilters, dries；
(3) alkali activation processing: zeolite dry in (2) is joined in the sodium hydroxide solution that 200ml concentration is 5% and carries out alkali activation processing 36 hours；Being washed out to pH value is 7.5, refilters, dries；
(4) reacting metal salt: zeolite dry in (3) is joined in the solution formed by 0.25mol aluminum nitrate, 0.2mol magnesium chloride and 150ml water, 24 hours response time；Then adjusting solution ph is after 6, then through washing, filters, dries 2 hours in 170 DEG C, obtains natural minerals loaded nano defluorinating agent.
Embodiment seven:
(1) high-temperature activation processes: carry out the natural zeolite that 100g particle diameter is 2mm under the high temperature that temperature is 650 DEG C processing 10 hours；
(2) acid activation processes: the zeolite after being processed by high-temperature activation joins and carries out acid activation process 14 hours in the sulfuric acid solution that 150ml concentration is 11%, and being washed out to pH value is 6.7, refilters, dries；
(3) alkali activation processing: zeolite dry in (2) is joined in the potassium hydroxide solution that 150ml concentration is 10% and carries out alkali activation processing 24 hours；Being washed out to pH value is 7.5, refilters, dries；
(4) reacting metal salt: zeolite dry in (3) is joined in the solution formed by 0.1mol aluminum nitrate, 0.05mol magnesium nitrate and 300ml water, 24 hours response time；Then adjusting solution ph is after 6, then through washing, filters, dries 3.5 hours in 160 DEG C, obtains natural minerals loaded nano defluorinating agent.
Above example is not limited only to protection scope of the present invention, all modifies based on the basic thought of the present invention or broadly falling in protection scope of the present invention of changing.
Claims (6)
1. the preparation method of a natural minerals loaded nano defluorinating agent, it is characterised in that: its step is as follows:
(1) high-temperature activation processes: the natural zeolite that particle diameter is 1-3mm is carried out high-temperature process；
(2) acid activation processes: the zeolite after being processed by high-temperature activation is that 1:1-2.5kg/L joins and carries out acid activation process in acid solution by mass volume ratio, and being washed out to pH value is 6-7, refilters, dry；
(3) alkali activation processing: be that 1:1-2.5kg/L joins and carries out alkali activation processing in aqueous slkali by mass volume ratio by zeolite dry in (2)；Being washed out to pH value is 7-8, refilters, dries；
(4) reacting metal salt: be that 1:1-3kg/L joins in metal salt solution and reacts 12-48 hour by mass volume ratio by zeolite dry in (3)；Then adjusting solution ph is after 5-6, then through washing, filtration, dries 1-10 hour to obtain natural minerals loaded nano defluorinating agent at 125-195 DEG C of temperature；Described metal ion is aluminium salt or the salt-mixture for aluminium salt and iron salt or the salt-mixture for aluminium salt and magnesium salt.
2. preparation method according to claim 1, it is characterised in that: in described step (1) temperature of high-temperature process be 400-1000 DEG C, the time be 3-20 hour.
3. preparation method according to claim 1, it is characterised in that: in described step (2) acid solution be in sulphuric acid or hydrochloric acid at least one be dissolved in deionized water formed the acid solution that concentration is 2-15%；The described acid activation process time is 6-48 hour.
4. preparation method according to claim 1, it is characterised in that: in described step (3), aqueous slkali is the aqueous slkali that concentration is 2-18% that at least one in sodium hydroxide, potassium hydroxide or ammonia is dissolved in deionized water to be formed；The described alkali activation processing time is 6-48 hour.
5. preparation method according to claim 1, it is characterised in that: in described step (4), in metal salt solution, the concentration of metal ion is 0.3-5mol/L.
6. preparation method according to claim 1, it is characterised in that: described aluminium salt is at least one in aluminum nitrate, aluminum sulfate or aluminum chloride；
Described iron salt is at least one in ferric nitrate, iron sulfate or iron chloride；
Described magnesium salt is at least one in magnesium nitrate, magnesium sulfate or magnesium chloride.
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| 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 |
| 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 |
| 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 |
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