CN104001479A - Inorganic mineral water treatment agent and preparation method thereof - Google Patents
Inorganic mineral water treatment agent and preparation method thereof Download PDFInfo
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- CN104001479A CN104001479A CN201410229891.8A CN201410229891A CN104001479A CN 104001479 A CN104001479 A CN 104001479A CN 201410229891 A CN201410229891 A CN 201410229891A CN 104001479 A CN104001479 A CN 104001479A
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Abstract
The invention belongs to the field of inorganic water treatment agents, and in particular relates to an inorganic mineral water treatment agent and a preparation method thereof. The water treatment agent is prepared from 50-60 parts of natural zeolite, 25-30 parts of red vesuvianite, 8-15 parts of natural fibers, 3-4 parts of ferrite and 1-2 parts of H2O2 water solution with the mass concentration of 35%; the preparation method comprises the following steps: mixing the natural zeolite with the vesuvianite, performing treatment of crushing, washing with acid, radiation in infrared light and the like, further mixing the natural fibers with a mixture of the zeolite and the vesuvianite in vacuum, adding a soluble ferrite solution, later adding the H2O2 water solution, stirring, drying, calcining at high temperature, cooling and drying, thereby obtaining the inorganic water treatment agent. The water treatment agent is relatively large in adsorption space and adsorption capacity, and can solve the problems that a conventional water treatment agent is poor in effect in treating sewage with complex components, can pollute the environment and the like. The water treatment agent provided by the invention is easy to regenerate, is free of secondary pollution, and can be widely applied to purification treatment on the sewage.
Description
Technical field
The present invention relates to water treatment agent field, be specifically related to a kind of inorganic mineral water treatment agent that natural zeolite and natural fiber be primary raw material and preparation method thereof of take.
Background technology
Water treatment agent be in water for industrial use, domestic water, wastewater treatment process the chemical agent that must use.The use of these chemical agents, makes water reach certain quality requirement.Its Main Function is the formation of controlling incrustation scale, mud, reduces foam, reduces the corrosion to material contact with water, and except suspended solid and the noxious material in anhydrating, deodorizing, decolouring, soften, stabilizing water quality and desalinization etc.The material base that the development of water treatment field itself relies on is also taken from environment, its many products also have many requirements that do not meet environmental protection, as the medicament of poisonous, high phosphorus, heavy metal or formulation product, the current technical demand that can't meet water treatment, therefore, water treatment field itself is also faced with the problems such as demand of technological innovation, development, develop low toxicity, even nontoxic with eco-friendly Green Water treatment product and rationally, economic, safe Green Water treatment process, be the active demand of current water treatment field.And zeolite has the performances such as adsorptivity, ion exchangeable, catalysis and acidproof heat-proof, can be used as adsorbent, ion-exchanger and catalyst, for aspects such as sewage disposals, there is market application foreground widely.
Natural zeolite surface silicon oxide structure has extremely strong hydrophily, and structural outer cation easily hydrolysis, the performance extreme difference that causes natural zeolite adsorb organic compound, and silicon-aluminum structure itself is electronegative, therefore natural zeolite is difficult to remove the anionic pollutant in water.Therefore, natural zeolite is carried out to modification, improve its adsorption capacity to organic matter and anion, can make natural zeolite more be widely used in water treatment field natural zeolite through modification, can obviously improve its porosity and surface-active, improve absorption property, ion-exchange performance and exchange capacity etc., thereby improve its use value.Modified zeolite comprises wide range, from through simple ion-exchange treatment until the complete avalanche of structure and the product that obtains all belongs to modified zeolite scope.
Porous zeolite material is to contain the crystalline zeolite that enriches porous, not only retained good acidity and the hydrothermal stability of zeolitic material, and because the introducing in new hole has improved it to macromolecular absorption and diffusion, at catalytic field, particularly relating in macromolecular catalytic reaction is the material that the utmost point has application prospect.Early stage porous zeolite synthetic method is mainly to use post processing, comprises hydrothermal treatment consists, acid treatment or alkali treatment.The use of template in recent years becomes the main method of synthesizing porous zeolite, mainly comprises mesoporous carbon template, high molecular polymer, organosilan and nano-inorganic substance etc.The shortcomings such as but existing template is big for environment pollution, cost is high, crystallization time is long, should not be widely used.
Chinese Patent Application No. 201210382889.5,201210010532.4 and 201310414937.9, by zeolite and other blend Coagulation and Adsorption or metal-modified, improve absorption and sedimentation effect, adding of metallics can change water quality activity, but the sorbent used natural materials that is, absorption property is limited, and metal-modified rear absorption object is single, the pollutants such as organic matter, metal can only partly be adsorbed, and adding of metal active material, can cause the secondary pollution to water body, the Treatment of Sludge trouble after absorption, easily causes secondary pollution to environment.
Chinese Patent Application No. 201310543704.9 and 200810143851.6, by zeolite through alkali treatment and surface modification, but the adsorptive selectivity having of modifier, can only adsorb certain or certain pollutant, so this inorganic agent of the processing of complicated component sewage is not had a significant effect.
Chinese Patent Application No. 201210020674.9 and 201110321285.5, by the alkali treatment of zeolite process, microwave treatment, acid treatment etc., make zeolite effective aperture increase and promote the generation of meso-hole structure, but inorganic agent used is the highly basic strong acid such as NaOH, lithium hydroxide, potassium hydroxide, sulfuric acid, nitric acid, has higher risk in large-scale production, and discharge of wastewater easily causes the secondary pollution of water quality, air etc.
Chinese Patent Application No. 200810080287.8 and 200810080287.8, uses template modified zeolite, and making the zeolite after modification is ordered porous material, but template is to mostly being non-Green Additives, easily, to environment, in manufacture process, crystallization time is long, makes production cost higher.
The problems such as the application of zeolite in sewage disposal is comparatively extensive, but that prior art exists is poor to the wastewater treatment efficiency of complicated component, adjuvant usedly easily water source is caused to secondary pollution, and cost of manufacture is high, technological process complexity.
Summary of the invention
The present invention is directed to the problems such as existing inorganic water treatment agent adsorbance is few, absorption affinity is little and environmental pollution, and cost of manufacture is high, complex process, it is the fiber multihole inorganic mineral water treatment agent that natural zeolite and natural fiber are made that a kind of main component is provided.
The present invention further provides a kind of preparation method of inorganic mineral water treatment agent, the method is by pulverizing natural zeolite, miniaturization natural fiber material, and under vacuum condition, evenly mix two kinds of materials, through high temperature sintering, natural fiber is stayed in zeolite space, make zeolite form fiber multihole shape structure, thereby improve the purified treatment ability of zeolite to sewage.
A kind of inorganic mineral water treatment agent of the present invention, is characterized in that weight portion consists of: the H that 50-60 part natural zeolite, the red pelelith of 25-30 part, 8-15 part natural fiber, 3-4 part ferrous salt and 1-2 part mass concentration are 35%
2o
2the aqueous solution forms, wherein said natural zeolite is selected at least one in analcime, phillipsite, sodalite, heulandite, clinoptilolite, chabasie, faujasite, described natural fiber is selected at least one in husk, stalk, flax, kapok, sugarcane, and described ferrous salt is selected FeSO
4, FeCl
2in a kind of.
Above-mentioned a kind of inorganic mineral water treatment agent, is characterized in that: described natural zeolite is preferably faujasite.
Above-mentioned a kind of inorganic mineral water treatment agent, is characterized in that: described ferrous salt and H
2o
2mass ratio is preferably m (Fe
2+)/m (H
2o
2)=8.
The preparation method of a kind of inorganic mineral water treatment agent of the present invention, is characterized in that: carry out as follows:
1) 50-60 part natural zeolite and the mixing of 25-30 part pelelith are crushed to particle diameter≤50 μ m, through ethylenediamine tetra-acetic acid, soak 2-5h, the salt acid elution that is 6M/L by concentration again, add hot reflux 8-10h, with distilled water, clean, dry 24h at 60 ~ 200 ℃, and the Infrared irradiation 3-6h that is 750nm with wavelength, be conducive to the formation of porous;
2), by the abundant miniaturization of 8-15 part natural fiber material, cross 2000 order molecular sieves, and ribbon length is less than 1) the middle particle diameter of processing rear gained material;
3) by 1) with 2) material of gained evenly mixes under 1.5-2.5MPa vacuum condition, make natural fiber enter into 1) the intragranular space of gained material, and calcine 3h-8h at Muffle furnace 700-1000 ℃, make 1) the fibrous porous structure of the interior formation of gained material, the moulding of fiber multihole zeolite matrix;
4) by 3) gained material adds in deionized water, then adds the ferrous salt of 3-4 part, is uniformly mixed, and drips 35% the H of 1-2 part in 0.5h-1.5h
2o
2the aqueous solution, at the uniform velocity stirs, and at 40-100 ℃, reacts 20h, and reaction finishes, centrifugal, filters, and using the precipitation obtaining as stock, by fluid bed, can make a kind of inorganic mineral water treatment agent.
The preparation method of above-mentioned a kind of inorganic mineral water treatment agent, is characterized in that: in manufacturing process step 3), in the de-airing mixer that mixture is 120r/min at rotating speed, evenly mix.
The preparation method of above-mentioned a kind of inorganic mineral water treatment agent, is characterized in that: the deionized water volume adding in step 4) in manufacturing process is the long-pending 0.8-1.5 of step 3) gains plastid times.
Natural zeolite and natural fiber for the present invention, via Infrared irradiation, vacuum is mixed, and the techniques such as high temperature sintering, make a kind of fiber multihole shape zeolite water inorganic agent; Component cost used is low, environmentally friendly, is easy to reclaim, and can be mass-produced.
Compared with prior art, usefulness is mainly reflected in the present invention:
(1) natural zeolite and natural fiber, through processing such as modification, vacuum mixing, make zeolite strengthen adsorbance increase, the absorption affinity of each pollutant;
(2) natural fiber of modified zeolite and miniaturization evenly mixes under vacuum condition, make fibrous matter enter into zeolite space, again via high temperature sintering, form the zeolite of fiber multihole shape structure, when effectively increasing specific area, changed pore size, made molecular weight, the material that is difficult for being adsorbed also can be removed, thereby reaches the effect to multiple pollutant high adsorption capacity;
(3) preparation technology of the present invention is simple, and cost is low, and is easy to reclaim, and can reuse environmental friendliness, suitable for mass production.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of a kind of inorganic mineral water treatment agent of the present invention.
The specific embodiment
Below by the specific embodiment, the present invention is described in further detail, but this should be interpreted as to scope of the present invention only limits to following example.In the situation that not departing from said method thought of the present invention, various replacements or the change according to ordinary skill knowledge and customary means, made, all should be within the scope of the present invention.
embodiment 1
1) the red pelelith of 10KG faujasite and 5KG is mixed to be crushed to particle diameter be 40 μ m, through ethylenediamine tetra-acetic acid, soak 3h, the salt acid elution that is 6M/L by concentration, add hot reflux 8h, with distilled water, clean again, dry 24h at 150 ℃, and the Infrared irradiation 6h that is 750nm with wavelength, be conducive to the formation of porous;
2), by the abundant miniaturization of 2KG dry straw, cross 2000 order molecular sieves, and ribbon length is 30 μ m;
3) by 1) with 2) material of gained evenly mixes under 2.5MPa vacuum condition, at 800 ℃ of Muffle furnaces, calcines 5h, makes 1) form fibrous porous structure, the moulding of fiber multihole zeolite matrix in gained material;
4) by 3) material to add volume be 3) step the deionized water of 1.5 times of material cumulative volumes in, then the 0.75KGFeSO adding
4, be uniformly mixed, in 1h, drip 0.3KG mass concentration and be 35% H
2o
2the aqueous solution; At the uniform velocity stir, at 100 ℃, react 20h; Reaction finishes, centrifugal, filters, and using the precipitation obtaining as stock, by fluid bed, can make a kind of inorganic mineral water treatment agent.
Embodiment 1 gained water treatment agent is added to certain water treatment plant import department sewage, water treatment agent of the present invention is joined in sewage by 0.30% of required water quality treatment amount.Before and after processing, water quality index is as following table:
| ? | Before processing (mg/L) | After processing (mg/L) |
| BOD (BOD 5） | 125 | 1.24 |
| Chemical oxygen consumption (COC) (COD cr） | 157 | 0.21 |
| Total nitrogen content (T-N) | 25.4 | 0.62 |
| Total phosphorus content (T-P) | 3.1 | Trace |
embodiment 2
1) the red pelelith of 5KG chabasie and 2.5KG is mixed to be crushed to particle diameter be 40 μ m, through ethylenediamine tetra-acetic acid, soak 3h, the salt acid elution that is 6M/L by concentration, add hot reflux 8h, with distilled water, clean again, dry 24h at 150 ℃, and the Infrared irradiation 6h that is 750nm with wavelength, be conducive to the formation of porous;
2), by the abundant miniaturization of the dry cane stalk of 2KG, cross 2000 order molecular sieves, and ribbon length is 35 μ m;
3) by 1) with 2) material of gained evenly mixes under 2.5MPa vacuum condition, at 800 ℃ of Muffle furnaces, calcines 5h, makes 1) form fibrous porous structure, the moulding of fiber multihole zeolite matrix in gained material;
4) by 3) material to add volume be 3) step the deionized water of 0.9 times of material cumulative volume in, then the 0.45KGFeSO adding
4, be uniformly mixed, in 1h, drip 0.15KG mass concentration and be 35% H
2o
2the aqueous solution; At the uniform velocity stir, at 100 ℃, react 20h; Reaction finishes, centrifugal, filters, and using the precipitation obtaining as stock, by fluid bed, can make a kind of inorganic mineral water treatment agent.
Embodiment 2 gained water treatment agents are added in certain papermaking sewage, water treatment agent of the present invention is joined in sewage by 0.95% of required water quality treatment amount.Before and after processing, water quality index is as following table:
| ? | Before processing (mg/L) | After processing (mg/L) |
| Suspension in water quality (SS) | 1067 | 25.7 |
| Chemical oxygen consumption (COC) (CODcr) | 4800 | 34 |
| Volatile phenol | 1.7 | Trace |
| Sulfide | 15.1 | Trace |
| Colourity | 96 | 8 |
embodiment 3
1) the red pelelith of 6KG sodalite and 3KG is mixed to be crushed to particle diameter be 40 μ m, through ethylenediamine tetra-acetic acid, soak 3h, the salt acid elution that is 6M/L by concentration, add hot reflux 8h, with distilled water, clean again, dry 24h at 150 ℃, and the Infrared irradiation 6h that is 750nm with wavelength, be conducive to the formation of porous;
2), by the abundant miniaturization of the dry cane stalk of 2KG, cross 2000 order molecular sieves, and ribbon length is 35 μ m;
3) by 1) with 2) material of gained evenly mixes under 2.5MPa vacuum condition, at 800 ℃ of Muffle furnaces, calcines 5h, makes 1) form fibrous porous structure, the moulding of fiber multihole zeolite matrix in gained material;
4) by 3) material to add volume be 3) step the deionized water of 0.8 times of material cumulative volume in, then the 1.8KGFeSO adding
4, be uniformly mixed, in 1h, drip 0.2KG mass concentration and be 35% H
2o
2the aqueous solution; At the uniform velocity stir, at 100 ℃, react 20h; Reaction finishes, centrifugal, filters, and using the precipitation obtaining as stock, by fluid bed, can make a kind of inorganic mineral water treatment agent.
Embodiment 3 gained water treatment agents are added in certain mine, steel ore deposit sewage, this water treatment agent is joined in sewage by 5% of required water quality treatment amount.Before and after processing, water quality index is as following table:
| ? | Cu（mg/L） | Fe（mg/L） | Cd（mg/L） | Pb（mg/L） | Zn（mg/L） | As（mg/L） | pH |
| Content before processing | 6294 | 26858 | 7 | 0.97 | 133 | 33 | <1.5 |
| Content after processing | Trace | 0.01 | Trace | Trace | Trace | Trace | 6.5 |
embodiment 4
1) 3KG chabasie and 3KG heulandite are mixed with the red pelelith of 3KG to be crushed to particle diameter be 50 μ m, through ethylenediamine tetra-acetic acid, soak 3h, the salt acid elution that is 6M/L by concentration, add hot reflux 8h, with distilled water, clean again, dry 24h at 200 ℃, and the Infrared irradiation 6h that is 750nm with wavelength, be conducive to the formation of porous;
2), by 1KG flax and the abundant miniaturization of 1KG kapok, cross 2000 order molecular sieves, and ribbon length is 40 μ m;
3) by 1) with 2) material of gained evenly mixes under 2MPa vacuum condition, at 1000 ℃ of Muffle furnaces, calcines 5h, makes 1) form fibrous porous structure, the moulding of fiber multihole zeolite matrix in gained material;
4) by 3) material to add volume be 3) step the deionized water of 0.8 times of material cumulative volume in, then the 0.5KGFeCl adding
2, be uniformly mixed, at 0.5h, drip the H that 0.25KG mass concentration is 35%
2o
2the aqueous solution; At the uniform velocity stir, at 80 ℃, react 20h; Reaction finishes, centrifugal, filters, and using the precipitation obtaining as stock, by fluid bed, can make a kind of inorganic mineral water treatment agent.
embodiment 5
1) 15KG phillipsite and 15KG clinoptilolite are mixed with the red pelelith of 20KG to be crushed to particle diameter be 50 μ m, through ethylenediamine tetra-acetic acid, soak 3h, the salt acid elution that is 6M/L by concentration, add hot reflux 8h, with distilled water, clean again, dry 24h at 180 ℃, and the Infrared irradiation 6h that is 750nm with wavelength, be conducive to the formation of porous;
2), by 6KG husk and the abundant miniaturization of 5KG kapok, cross 2000 order molecular sieves, and ribbon length is 35 μ m;
3) by 1) with 2) material of gained evenly mixes under 2MPa vacuum condition, at 850 ℃ of Muffle furnaces, calcines 8h, makes 1) form fibrous porous structure, the moulding of fiber multihole zeolite matrix in gained material;
By 3) material to add volume be 3) step the deionized water of 0.8 times of material cumulative volume in, then add the FeSO by 1.0KG
4with 0.8 KG FeCl
2, be uniformly mixed, in 1.5h, drip 1.5KG mass concentration and be 35% H
2o
2the aqueous solution; At the uniform velocity stir, at 100 ℃, react 20h; Reaction finishes, centrifugal, filters, and using the precipitation obtaining as stock, by fluid bed, can make a kind of inorganic mineral water treatment agent.
Claims (6)
1. an inorganic mineral water treatment agent, is characterized in that weight portion consists of: the H that 50-60 part natural zeolite, the red pelelith of 25-30 part, 8-15 part natural fiber, 3-4 part ferrous salt and 1-2 part mass concentration are 35%
2o
2the aqueous solution forms, wherein said natural zeolite is selected at least one in analcime, phillipsite, sodalite, heulandite, clinoptilolite, chabasie, faujasite, described natural fiber is selected at least one in husk, stalk, flax, kapok, sugarcane, and described ferrous salt is selected FeSO
4, FeCl
2in a kind of.
2. according to a kind of inorganic mineral water treatment agent described in claim 1, it is characterized in that: described natural zeolite is preferably faujasite.
3. according to a kind of inorganic mineral water treatment agent described in claim 1, it is characterized in that: described ferrous salt and H
2o
2mass ratio is preferably m (Fe
2+)/m (H
2o
2)=8.
4. a preparation method for inorganic mineral water treatment agent, is characterized in that: carry out as follows:
1) 50-60 part natural zeolite and the mixing of 25-30 part pelelith are crushed to particle diameter≤50 μ m, through ethylenediamine tetra-acetic acid, soak 2-5h, the salt acid elution that is 6M/L by concentration again, add hot reflux 8-10h, with distilled water, clean, dry 24h at 60 ~ 200 ℃, and the Infrared irradiation 3-6h that is 750nm with wavelength, be conducive to the formation of porous;
2), by the abundant miniaturization of 8-15 part natural fiber material, cross 2000 order molecular sieves, and ribbon length is less than 1) the middle particle diameter of processing rear gained material;
3) by 1) with 2) material of gained evenly mixes under 1.5-2.5MPa vacuum condition, make natural fiber enter into 1) the intragranular space of gained material, and calcine 3h-8h at Muffle furnace 700-1000 ℃, make 1) the fibrous porous structure of the interior formation of gained material, the moulding of fiber multihole zeolite matrix;
4) by 3) gained material adds in deionized water, then add 3-4 part ferrous salt, and be uniformly mixed, in 0.5h-1.5h, drip the H of 1-2 part 35%
2o
2the aqueous solution, at the uniform velocity stirs, and at 40-100 ℃, reacts 20h, and reaction finishes, centrifugal, filters, and using the precipitation obtaining as stock, by fluid bed, can make a kind of inorganic mineral water treatment agent.
5. according to the preparation method of a kind of inorganic mineral water treatment agent described in claim 3, it is characterized in that: in manufacturing process step 3), in the de-airing mixer that mixture is 120r/min at rotating speed, evenly mix.
6. according to the preparation method of a kind of inorganic mineral water treatment agent described in claim 4, it is characterized in that: the deionized water volume adding in step 4) in manufacturing process is the long-pending 0.8-1.5 of step 3) gains plastid times.
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Cited By (6)
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| CN104383896A (en) * | 2014-10-31 | 2015-03-04 | 田琳琳 | Composite material for purifying industrial waste water |
| CN104383897A (en) * | 2014-10-31 | 2015-03-04 | 田琳琳 | Adsorbing material for treating wastewater |
| CN106268662A (en) * | 2016-08-25 | 2017-01-04 | 贵州万山兴隆锰业有限公司 | A kind of manganese ore waste water adsorbing material and preparation method thereof |
| CN106396920A (en) * | 2016-08-31 | 2017-02-15 | 华艺生态园林股份有限公司 | Manufacture method of organic ground surface mulch for garden trees |
| CN111087199A (en) * | 2019-12-20 | 2020-05-01 | 南通斐腾新材料科技有限公司 | Preparation method of porous hollow zeolite particles for adsorbing VOCs (volatile organic compounds) |
| CN114471452A (en) * | 2022-03-04 | 2022-05-13 | 太原碧蓝水利工程设计股份有限公司 | Method for rapidly treating acidic mine water and adsorbent prepared from acidic mine water |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383896A (en) * | 2014-10-31 | 2015-03-04 | 田琳琳 | Composite material for purifying industrial waste water |
| CN104383897A (en) * | 2014-10-31 | 2015-03-04 | 田琳琳 | Adsorbing material for treating wastewater |
| CN106268662A (en) * | 2016-08-25 | 2017-01-04 | 贵州万山兴隆锰业有限公司 | A kind of manganese ore waste water adsorbing material and preparation method thereof |
| CN106396920A (en) * | 2016-08-31 | 2017-02-15 | 华艺生态园林股份有限公司 | Manufacture method of organic ground surface mulch for garden trees |
| CN111087199A (en) * | 2019-12-20 | 2020-05-01 | 南通斐腾新材料科技有限公司 | Preparation method of porous hollow zeolite particles for adsorbing VOCs (volatile organic compounds) |
| CN114471452A (en) * | 2022-03-04 | 2022-05-13 | 太原碧蓝水利工程设计股份有限公司 | Method for rapidly treating acidic mine water and adsorbent prepared from acidic mine water |
| CN114471452B (en) * | 2022-03-04 | 2023-09-08 | 太原碧蓝水利工程设计股份有限公司 | Method for rapidly treating acidic mine pit water and adsorbent prepared from acidic mine pit water |
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| CN104001479B (en) | 2015-11-18 |
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