CN1698948A - Water purificant using paligorskite and sepiolite as supporter, its preparation and application method - Google Patents
Water purificant using paligorskite and sepiolite as supporter, its preparation and application method Download PDFInfo
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- CN1698948A CN1698948A CN 200510049651 CN200510049651A CN1698948A CN 1698948 A CN1698948 A CN 1698948A CN 200510049651 CN200510049651 CN 200510049651 CN 200510049651 A CN200510049651 A CN 200510049651A CN 1698948 A CN1698948 A CN 1698948A
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- sepiolite
- water
- palygorskite
- scavengine agent
- dehydration
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Abstract
This invention discloses a water scavengine agent, in addition to its preparing and using method. It embarks trivalent iron ion and its hydroxide in the mine crystal lattice of paligorskite and meerschaum, wherein the weight percentage of iron of the catalyst is 1~25%. Said agent has a big absorption capability to anion contaminant and errant algae with minus charge in its surface; in addition, it can restrain water eutrophication and kill errant algae; when red current happens, it can make algae sinking to sea, so to block the red current from the cultivate marine site.
Description
Technical field
The present invention relates to chemistry or physical method, relating in particular to a kind of is water scavengine agent and the preparation and the using method of carrier with palygorskite, sepiolite.
Background technology
The body eutrophication that industrial wastewater and sanitary wastewater discharging are caused is very harmful to aquaculture, it is to cause fish, shrimp, shellfish morbidity main causes of death, and the ecological balance in the water environment in the excessive breeding serious threat of the planktonic algae relevant with eutrophication.The frequent red tide that takes place in China offshore sea waters can cause the large tracts of land death of fishes and shrimps, shellfish.Exploitation is used to suppress body eutrophication trend, the planktonic algae of drawing up breeding, the water scavengine agent of killing the red tide algae have important economic implications and environmental ecological benefit.
Summary of the invention
The purpose of this invention is to provide a kind of is water scavengine agent and the preparation and the using method of carrier with palygorskite, sepiolite.
With palygorskite, sepiolite is the water scavengine agent of carrier: in the mineral lattice of palygorskite, sepiolite and surperficial appendix ferric ion and hydroxide thereof are arranged, by weight percentage, the content of ferro element in catalyst is 1～25%.
Said palygorskite, sepiolite are the magnesium silicate mineral with layer chain structure, and the molecular formula of palygorskite is:
Mg
5Si
8O
20(OH)
2(OH
2)
44H
2The molecular formula of O sepiolite is:
Mg
8Si
12O
30(OH)
4(OH
2)
48H
2They are clay, mud stone, shale or massive ore in natural output form for O.
With palygorskite, sepiolite is that the preparation method of the water scavengine agent of carrier may further comprise the steps:
1) through separate purifying, and to be crushed to less than 300 purpose palygorskites, sepiolite and weight be that 3～8 times acid solution mixes, and stirs, reacted 30～50 hours, continue to stir during this time, centrifugal then or filtering means dehydration, water cleaning～dehydration 3～5 times is to remove remaining acid solution;
2) mixture dehydration back is 3～5 times in an ore with weight, to be that 1～5 mole iron salt solutions is mixed evenly react 40～60 hours concentration, during stir several, when stirring, slowly add concentration then and be 0.5～5 mole NaOH or ammonia spirit, make the pH of mixed value be not less than 6;
3) mixed liquor is filtered or centrifugal dehydration, water cleans 2～3 times, and filter-press dehydration is perhaps dried being lower than under 80 ℃ of temperature, and is ground to less than 300 orders, and products therefrom is water scavengine agent.
Said acid solution is that concentration is 3～5 moles hydrochloric acid, nitric acid or sulfuric acid.
Said molysite is a kind of in ferric trichloride, ferric nitrate, ferric sulfate and the hydrate thereof or several.
The water scavengine agent that the present invention proposes be applicable to red tide algae in titanium pigment, nitrate nitrogen, nitrite nitrogen, planktonic algae and the seawater of removing in the aquatic farm water body, it is 5%～25% suspension that water scavengine agent is mixed with concentration, by the consumption of every square metre of water surface 0.5～5 gram water scavengine agent suspension is sprayed in the water body to get final product.
The water scavengine agent that the present invention proposes adopts natural palygorskite, the sepiolite carrier as iron ion and iron hydroxide, and it has wide material sources, cheap advantage.On the preparation method, the present invention adopts the selectivity corrosion to remove the cation of palygorskite lattice octahedral site, by the ion exchange reaction iron ion is implanted palygorskite, the sepiolite lattice, and in mineral surfaces formation ferric hydroxide precipitate, the positive charge of surplus in the mineral, and the electropositive of ferric hydroxide colloid, make it to the anionic pollutant in the water body, and the surperficial planktonic algae that has negative electrical charge has very strong adsorption capacity, have concurrently and suppress body eutrophication and kill the planktonic algae double effects, be suitable for the aquaculture industry, the water body purification of especially high-grade aquaculture factory, conventional use can purify water, the generation of prevention aquatic products disease.When red tide takes place, it is sprayed at the red tide marine site, can make algae sink to seabed death at short notice, red tide can be blocked in and culture outside the marine site.
The specific embodiment
Palygorskite and sepiolite are the natural magnesium silicate mineral with chain layer structure.Their outer formation is fibrous, diameter 10～100 nanometers, and several microns to tens microns of length, from the monocrystalline size, it meets the definition of nano material, belongs to typical natural 1-dimention nano mineral.
The molecular formula of palygorskite is:
Mg
5Si
8O
20(OH)
2(OH
2)
4·4H
2O
The molecular formula of sepiolite is:
Mg
8Si
12O
30(OH)
4(OH
2)
48H
2Their common traits on crystalline texture of O are, accompany a Mg-O (OH) octahedral layer between per two Si-O tetrahedral layers, form basic structural unit, basic structural unit is staggered, formed the hole, tunnel that is parallel to lattice direction, hole, palygorskite intracrystalline tunnel cross section is 0.37 * 0.64 nanometer, and the tunnel hole dimension of sepiolite similarly.The hole, intracrystalline tunnel of nano-scale makes palygorskite and sepiolite have huge specific area and absorption～catalytic activity, and this is the basis that it is suitable for being used as the water scavengine agent carrier.
Palygorskite, sepiolite be general and impure mineral symbiosis at nature, tight agglomeration each other, and the output form is clay, mud stone, shale or loose massive ore.Use known technology to separate purify natural palygorskite (having another name called attapulgite) and sepiolite among the present invention, it comprises that pulverizings, making beating make suspension, classification collection less than the particle of 5 μ etc.This palygorskite, sepiolite through purifying is the clay mineral of a kind of light gray, light green color tool layered crystal structure.Separate purification process and can select conventional mining equiment for use.
Preparation method's the first step is to be crushed to less than 300 purpose palygorskites, sepiolite and acid solution reaction, can to use hydrochloric acid, nitric acid or sulfuric acid, to take all factors into consideration from environment and cost factor, recommends to use hydrochloric acid.Impure mineral remaining in the ore can be dissolved by acid, as carbonate, partial clay mineral, iron and manganese oxides and silicate hydroxide minerals.Should adjust the concentration and the consumption of acid during practical operation according to composition of ores, the ore that the solubility in acid impurity content is high can improve the concentration of acid or increase with the acid amount.In the acid treatment process, the cation of octahedral site in palygorskite, the sepiolite lattice (refers to remove Si
4+Other cation in addition) tend to by the selectivity corrosion, these cationic lattice positions are by H
+Ion replaces.Mixture can be heated to 60～90 ℃ in the molten process of acid, so that accelerate reaction process.Should dewater and wash after acid is molten, remove remaining acid.
Preparation method's second step is to use by iron salt solutions carries out ion exchange to palygorskite, sepiolite.Palygorskite, sepiolite and after iron salt solutions mixed, the ferric ion in the solution entered the octahedral site of mineral lattice make palygorskite recover the structure of acid before molten.Anion in the salt is little to ion exchange reaction influence, can be whether according to the facility of raw material sources, and price factor is selected ferric hydrochloride, nitrate or sulfate.With NaOH or ammoniacal liquor solution being neutralized after the ion exchange is in order to make the form precipitation of iron ion remaining in the solution with hydroxide, to improve its utilization rate and to reduce discharging.Should dewater and wash after the neutralization, to remove formed sodium salt or ammonia salt.
Can directly pack behind the product filter-press dehydration and put goods on the market, because of the moisture content height, can increase cost of transportation, but save the energy consumption of drying course, also avoid causing adsorption activity to descend because of bake out temperature is too high.Half-dried attitude product is put on market, should in external packing, indicate solids content and water content.For long-distance transportation, it is more suitable that the back pack is ground in oven dry.Notice that bake out temperature should not surpass 80 ℃, otherwise will cause the adsorption activity of product to reduce.
By the water scavengine agent of the above method preparation anionic pollutant in can adsorbed water body,, be because the Mg in the palygorskite, sepiolite lattice as titanium pigment, nitrate nitrogen and nitrite nitrogen
2+Ion is by Fe
3+After the ion exchange, change the distribution of charges of mineral lattice, made its surface have positive charge, and be wrapped in the Fe (OH) of mineral surfaces
3Also have positive colloidal nature, they produce synergy, and the relatively large anion of volume in the water body is had stronger suction-operated; It is to planktonic algae, and especially the absorption of red tide algae is because the surface of these algae has negative electrical charge.After this water scavengine agent was sprayed in the waters of algal bloom, the very fast gathering of algae was agglomerating, and the back that sinks under water is dead.
Further specify the present invention below in conjunction with instantiation.
Embodiment 1:
1) take by weighing 10 kilograms and be crushed to, add 30 kilograms of concentration and be 5 moles hydrochloric acid solution, stir, reacted 30 hours less than 300 purpose palygorskites, during continue to stir, centrifugal then or filtering means dehydration, water cleaning～dehydration 5 times is to remove remaining acid solution;
2) getting 30 kilograms of concentration that configured is 5 moles liquor ferri trichloridi, evenly mixed with the palygorskite after the acid treatment, reacted 40 hours, stir during this time for several times, when stirring, slowly add concentration then and be 0.5 mole NaOH solution, with pH meter observation pH value, equal till 6 simultaneously until the pH of mixed value;
3) with the mixed liquor centrifugal dehydration, water cleans 3 times, packs behind the filter-press dehydration.
Embodiment 2:
1) take by weighing 10 kilograms and be crushed to, add 80 kilograms of concentration and be 3 moles sulfuric acid solution, stir, reacted 50 hours less than 300 purpose sepiolites, during continue to stir, centrifugal then or filtering means dehydration, water cleaning～dehydration 3 times is to remove remaining acid solution;
2) getting 50 kilograms of concentration that configured is 1 mole ferrum sulfuricum oxydatum solutum, evenly mixed with the sepiolite after the acid treatment, reacted 40 hours, stir during this time for several times, when stirring, slowly add concentration then and be 5 moles ammonia spirit, with pH meter observation pH value, equal till 6 simultaneously until the pH of mixed value;
3) with the mixed liquor centrifugal dehydration, water cleans 5 times, and dry under 60 ℃ of temperature the dehydration back, is ground to less than 300 orders to pack.
Embodiment 3:
1) take by weighing 10 kilograms and be crushed to, add 50 kilograms of concentration and be 3 moles salpeter solution, stir, reacted 40 hours less than 300 purpose palygorskites, during continue to stir, centrifugal then or filtering means dehydration, water cleaning～dehydration 5 times is to remove remaining acid solution;
2) getting 50 kilograms of concentration that configured is 3 moles iron nitrate solution, evenly mixed with the palygorskite after the acid treatment, reacted 60 hours, stir during this time for several times, when stirring, slowly add concentration then and be 1 mole ammonia spirit, with pH meter observation pH value, equal till 6 simultaneously until the pH of mixed value;
3) with the mixed liquor centrifugal dehydration, water cleans 4 times, and dry under 70 ℃ of temperature the dehydration back, is ground to less than 300 orders to pack.
Embodiment 4:
1) take by weighing 10 kilograms and be crushed to, add 80 kilograms of concentration and be 3 moles hydrochloric acid solution, stir, reacted 50 hours less than 300 purpose sepiolites, during continue to stir, centrifugal then or filtering means dehydration, water cleaning～dehydration 5 times is to remove remaining acid solution;
2) getting 30 kilograms of concentration that configured is 2 moles iron nitrate solution, evenly mixed with the palygorskite after the acid treatment, reacted 60 hours, stir during this time for several times, when stirring, slowly add concentration then and be 5 moles ammonia spirit, with pH meter observation pH value, equal till 6 simultaneously until the pH of mixed value;
3) with the mixed liquor centrifugal dehydration, water cleans 3 times, packs behind the filter-press dehydration.
Embodiment 5:
Get 1 kilogram of embodiment 1 product (moisture 15%), add ten kilograms in water, stir and make suspension, can spray 170～1700 square metres of water surfaces for aquaculture, to remove nutritive salt and planktonic algae.
Embodiment 6:
Get 1 kilogram of embodiment 2 product, add 24 kilograms in water, stir and make suspension, can spray 200～2000 square metres of seas, to remove the red tide algae.
The water scavengine agent that the present invention proposes is a primary raw material with natural palygorskite, sepiolite, and it has wide material sources, cheap advantage.This water scavengine agent preparation technology is simple, easy to use, to the anionic pollutant in the water body, and the surperficial planktonic algae that has negative electrical charge has very strong adsorption capacity, have concurrently and suppress body eutrophication and kill the planktonic algae double effects, be suitable for the aquaculture industry, the water body purification of especially high-grade aquaculture factory, conventional use can purify water, the generation of prevention aquatic products disease.When red tide takes place, it is sprayed at the red tide marine site, can make algae sink to seabed death at short notice, red tide can be blocked in and culture outside the marine site.
Claims (6)
1. one kind is the water scavengine agent of carrier with palygorskite, sepiolite, it is characterized in that in the mineral lattice of palygorskite, sepiolite and surperficial appendix has ferric ion and hydroxide thereof, by weight percentage, the content of ferro element in catalyst is 1～25%.
2. according to claim 1 a kind of be the water scavengine agent of carrier with palygorskite, sepiolite, it is characterized in that said palygorskite, sepiolite are the magnesium silicate mineral with layer chain structure, the molecular formula of palygorskite is:
Mg
5Si
8O
20(OH)
2(OH
2)
4·4H
2O
The molecular formula of sepiolite is:
Mg
8Si
12O
30(OH)
4(OH
2)
4·8H
2O
They are clay, mud stone, shale or massive ore in natural output form.
One kind as claimed in claim 1 be the preparation method of the water scavengine agent of carrier with palygorskite, sepiolite, it is characterized in that it may further comprise the steps:
1) through separate purifying, and to be crushed to less than 300 purpose palygorskites, sepiolite and weight be that 3～8 times acid solution mixes, and stirs, reacted 30～50 hours, continue to stir during this time, centrifugal then or filtering means dehydration, water cleaning～dehydration 3～5 times is to remove remaining acid solution;
2) mixture dehydration back is 3～5 times in an ore with weight, to be that 1～5 mole iron salt solutions is mixed evenly react 40～60 hours concentration, during stir several, when stirring, slowly add concentration then and be 0.5～5 mole NaOH or ammonia spirit, make the pH of mixed value be not less than 6;
3) mixed liquor is filtered or centrifugal dehydration, water cleans 2～3 times, and filter-press dehydration is perhaps dried being lower than under 80 ℃ of temperature, and is ground to less than 300 orders, and products therefrom is water scavengine agent.
4. according to claim 3 a kind of be the preparation method of the water scavengine agent of carrier with palygorskite, sepiolite, it is characterized in that said acid solution is that concentration is 3～5 moles hydrochloric acid, nitric acid or sulfuric acid.
5. according to claim 3 a kind of be the preparation method of the water scavengine agent of carrier with palygorskite, sepiolite, it is characterized in that said molysite is a kind of in ferric trichloride, ferric nitrate, ferric sulfate and the hydrate thereof or several.
One kind as claimed in claim 1 be the using method of the water scavengine agent of carrier with palygorskite, sepiolite, it is characterized in that it is used for removing red tide algae in titanium pigment, nitrate nitrogen, nitrite nitrogen, planktonic algae and the seawater of aquatic farm water body, it is 5%～25% suspension that water scavengine agent is mixed with concentration, by the consumption of every square metre of water surface 0.5～5 gram water scavengine agent suspension is sprayed in the water body to get final product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510049651 CN1698948A (en) | 2005-04-25 | 2005-04-25 | Water purificant using paligorskite and sepiolite as supporter, its preparation and application method |
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|---|---|---|---|
| CN 200510049651 CN1698948A (en) | 2005-04-25 | 2005-04-25 | Water purificant using paligorskite and sepiolite as supporter, its preparation and application method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306344B (en) * | 2008-01-25 | 2010-07-21 | 西北师范大学 | Modified lassalite supported belta-cyclodextrin compound absorbent and preparation method and use thereof |
| CN101306343B (en) * | 2007-11-14 | 2010-09-22 | 中国科学院南京土壤研究所 | Method for preparing water body dephosphorized granule adsorbent using attapulgite clay |
| CN102553519A (en) * | 2010-12-10 | 2012-07-11 | 北京师范大学 | Iron modified attapulgite adsorbent, its preparation method and application thereof |
| CN102872844A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Composite adsorption material for removing gallium ions from natural water and preparation method for adsorption material |
| CN103446995A (en) * | 2012-05-30 | 2013-12-18 | 王金生 | Method for adsorption treatment of cesium-containing wastewater through using iron modified attapulgite adsorbent |
| CN103446994A (en) * | 2012-05-30 | 2013-12-18 | 李剑 | Method for adsorption treatment of uranium-containing wastewater through using iron modified attapulgite adsorbent |
| CN104525103A (en) * | 2014-12-31 | 2015-04-22 | 中国地质大学（武汉） | Magnetic iron oxide/sepiolite nanocomposite and preparation method and application thereof |
| CN108355624A (en) * | 2018-04-28 | 2018-08-03 | 广东国宇环保科技有限公司 | Based on dolomitic limestone-iron oxide-Nano chitosan composite material of steamed bun group Minerals And Rocks and its preparation and application |
| CN109516538A (en) * | 2017-09-19 | 2019-03-26 | 宇部材料工业株式会社 | Red tide expellent and the red tide expelling method for using it |
| CN110698225A (en) * | 2019-09-10 | 2020-01-17 | 四川大学 | Modified ceramsite with phosphorus control and algae inhibition functions and preparation method and application thereof |
| CN114364639A (en) * | 2019-06-20 | 2022-04-15 | 株式会社杉田制线 | Water purification material having iron as main component and method for manufacturing the same |
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2005
- 2005-04-25 CN CN 200510049651 patent/CN1698948A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306343B (en) * | 2007-11-14 | 2010-09-22 | 中国科学院南京土壤研究所 | Method for preparing water body dephosphorized granule adsorbent using attapulgite clay |
| CN101306344B (en) * | 2008-01-25 | 2010-07-21 | 西北师范大学 | Modified lassalite supported belta-cyclodextrin compound absorbent and preparation method and use thereof |
| CN102553519A (en) * | 2010-12-10 | 2012-07-11 | 北京师范大学 | Iron modified attapulgite adsorbent, its preparation method and application thereof |
| CN103446995A (en) * | 2012-05-30 | 2013-12-18 | 王金生 | Method for adsorption treatment of cesium-containing wastewater through using iron modified attapulgite adsorbent |
| CN103446994A (en) * | 2012-05-30 | 2013-12-18 | 李剑 | Method for adsorption treatment of uranium-containing wastewater through using iron modified attapulgite adsorbent |
| CN102872844A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Composite adsorption material for removing gallium ions from natural water and preparation method for adsorption material |
| CN104525103A (en) * | 2014-12-31 | 2015-04-22 | 中国地质大学（武汉） | Magnetic iron oxide/sepiolite nanocomposite and preparation method and application thereof |
| CN104525103B (en) * | 2014-12-31 | 2016-08-31 | 中国地质大学（武汉） | Magnetic iron oxide/meerschaum nano composite material and its production and use |
| CN109516538A (en) * | 2017-09-19 | 2019-03-26 | 宇部材料工业株式会社 | Red tide expellent and the red tide expelling method for using it |
| CN108355624A (en) * | 2018-04-28 | 2018-08-03 | 广东国宇环保科技有限公司 | Based on dolomitic limestone-iron oxide-Nano chitosan composite material of steamed bun group Minerals And Rocks and its preparation and application |
| CN114364639A (en) * | 2019-06-20 | 2022-04-15 | 株式会社杉田制线 | Water purification material having iron as main component and method for manufacturing the same |
| CN110698225A (en) * | 2019-09-10 | 2020-01-17 | 四川大学 | Modified ceramsite with phosphorus control and algae inhibition functions and preparation method and application thereof |
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