CN105642241A - Biomass-based adsorption material for removing harmful anions in water and preparation method thereof - Google Patents
Biomass-based adsorption material for removing harmful anions in water and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a biomass-based adsorption material for removing anions in water and a preparation method thereof. Inorganic magnetic particles containing iron and/or inorganic particles containing aluminum are loaded on the surface of the biomass-based adsorption material; the main raw material of the biomass-based adsorption material is agricultural waste; the harmful anion comprises F-，AsO2 -And AsO4 3-. Compared with the harmful anion adsorbing material in the prior art, the invention adopts the biomass agricultural waste material as the adsorbing substrate, has simple process and convenient operation, and is suitable for the water pollution treatment of various harmful anions. The production scale can be large or small, which is not only beneficial to be popularized in remote rural areas and individual users, but also suitable for large-scale water treatment.
Description
Technical field
The present invention relates to the technical field of water treatment sorbing material. More specifically, it relates to a kind of for except the biomass-based sorbing material of the middle harmful anion that anhydrates and its preparation method.
Background technology
Negatively charged ion harmful in water has fluorion, containing arsenic negatively charged ion etc. Fluorine is the essential element of mammalian tooth and bone growth, but the fluorine of excess intake can cause dental fluorosis, skeletal fluorosis, and the disease of some neural system. The absorption of arsenic can cause cardiovascular disorder and nervous system disorders, also can significantly improve the probability of lung, liver, kidney, bladder, skin canceration. China belongs in the world one of poor-water country that water resources is less per capita, the insufficient water in a lot of city, in addition Drinking Water in China is of low quality, and whole nation rural area more than several hundred million people is still drinking defective water so that the cancer morbidity in some area is far above mean level (ML). Along with the high speed development of economy, the quantity discharged cumulative year after year of China's trade effluent, these harmful anions can be discharged in water system by forms such as trade effluents, and therefore the removal of harmful anion has become an important aspect of water treatment. Meanwhile, biological material especially some farm crop be the very high resource of annual production, but a lot of agriculture waste biological material utilization ratio is not high, its processing mode even contaminate environment. Therefore, Appropriate application biological material especially some agricultural wastes resources have very important significance.
The method of a lot of physics and chemistry can be used for except the harmful anion in anhydrating, such as biological process, reverse osmosis method, ion exchange method, electrochemical deposition method, film engineering method, absorption method etc. Wherein absorption method owing to adsorbent species is various, be easy to process, can regenerate, efficiently and it would furthermore be possible to realize low cost and become the most frequently used method. Biomass-based material for water treatment especially cellulose base material for water treatment had and study comparatively widely and carry out. Wherein cellulose base chemistry modified water process material mainly utilizes the chemical structure feature of Mierocrystalline cellulose containing great amount of hydroxy group etc. itself, by the chemical reaction under the condition such as initiator, catalyzer, introduce or some compounds of grafting, utilize the functional group in these compounds can produce the adsorption of the physical chemistry such as electrostatic attraction, complexing with the negatively charged ion containing negative electricity group in water, thus except the harmful anion in anhydrating. But, the preparation process of these materials is mostly comparatively complicated, and cost is relatively high.
It is thus desirable to provide a kind of cost is low, drawing materials conveniently, preparation technology is simply for except the biomass-based sorbing material of the middle harmful anion that anhydrates and its preparation method.
Summary of the invention
It is an object of the present invention to provide a kind of green, with low cost, efficient for except the middle F that anhydrates-, AsO2 -, AsO4 3-Deng the biomass-based sorbing material of harmful anion, this sorbing material load has the inorganic particle containing iron and the inorganic particulate containing aluminium, can effectively except the middle harmful anion that anhydrates, biomass-based sorbing material described in simultaneously has wider adsorption range, is adsorbed with clearer and more definite specific aim for harmful anion in different water body.
Another object of the present invention is to provide a kind of preparation method for the biomass-based sorbing material except the middle harmful anion that anhydrates.
For achieving the above object, the present invention adopts following technical proposals:
For the biomass-based sorbing material except the middle harmful anion that anhydrates, the area load inorganic particulate of described biomass-based sorbing material; The main raw material of described biomass-based sorbing material is agricultural wastes; Described harmful anion comprises F-, AsO2 -And AsO4 3-;
Described inorganic particulate is the inorganic particle containing iron and/or the inorganic particulate containing aluminium.
The present invention is used for the biomass-based sorbing material except the middle harmful anion that anhydrates, and is select agricultural wastes as the biomass body material of described sorbing material; Area load at biomass body material contains the inorganic particle of iron and/or the inorganic particulate containing aluminium, thus make biomass substrate material surface with iron-aluminium (hydrogen) oxide inorganic particle, the inorganic particulate of institute's load can with the physical and chemical adsorption effect such as the harmful anion generation complexing in water, the harmful anion in water is removed.
Compared with anion adsorbent material of the prior art, the present invention adopts the biomass agricultural wastes of natural cheapness as sorbing material matrix, utilize co-precipitation " one kettle way " can simultaneously load iron content magnetic inorganic particle and containing the inorganic particulate of aluminium, with low cost, easy and simple to handle; Utilize different inorganic particulates different for the negatively charged ion nuisance adsorption selectivity of different sorts in water, different valence state simultaneously, the sorbing material adsorption range of this kind of biomass-based multiple inorganic particulate load is wider, can also regulate and control according to the different ratio to the inorganic particulate of load on biomass matrix of the negatively charged ion nuisance content in different water body, thus make material to the absorption of the negatively charged ion nuisance in different water body more targetedly, control; In addition, this kind of biomass-based multiple inorganic particulate sorbing material can keep the advantage of the magnetic particle of iron content, and under externally-applied magnetic field, sorbing material is easy to be separated with water simply and rapidly.
Described harmful anion mainly refers to F-, AsO2 -, AsO4 3-Deng.
Preferably, the amount of described carrying inorganic particle and the ratio of biomass matrix are 0.005mol/g-0.5mol/g.
Preferably, the described inorganic particle containing iron is Fe3O4Inorganic particle; The described inorganic particulate containing aluminium is Al (OH)3Inorganic particulate.
Preferably, the raw material of described biomass-based sorbing material is selected from herbaceous plant or xylophyta.
Preferably, the mixing of one or more that described herbaceous plant is selected from the grass bits on agricultural crop straw, reed, reed reed, awns bar, bamboo or lawn;
More preferably, the mixing of one or more that described agricultural crop straw is selected from wheat straw, straw, maize straw, soybean stalk, cotton stalk or sweet potato vine.
Preferably, described xylophyta is selected from fallen leaves or the wood chip of trees.
For a preparation method for the biomass-based sorbing material except the middle harmful anion that anhydrates, comprise following preparation process:
(1) by the raw material of biomass-based sorbing material by mechanical disintegration, pulverizing into the powder of 100 ��m of-10mm, the biological material powder obtained is as sorbing material matrix;
(2) when protection, the stirring of rare gas element, step (1) is obtained biological material powder and containing Fe2+��Fe3+, and/or Al3+The aqueous solution join in reactor, under certain temperature, ammoniacal liquor is slowly added above-mentioned reactor and reacts; After reaction terminates, magnetic resolution reaction product, through washing, dry, obtain for the biomass-based sorbing material except the middle harmful anion that anhydrates.
Preferably, described containing Fe2+��Fe3+, and/or Al3+Water in Fe2+Content is 0.025mol/L-0.5mol/L; Fe3+Content is 0.05mol/L-1.0mol/L; Al3+Content is 0.05mol/L-1.0mol/L; The concentration of described ammoniacal liquor is 25%, and ammoniacal liquor is 0.5mol/L-10mol/L relative to the add-on of the aqueous solution.
Preferably, the temperature of reaction described in step (2) is 20 DEG C-100 DEG C, and step (2) the described reaction times is 1-24 hour.
The above-mentioned application for the biomass-based sorbing material except the middle harmful anion that anhydrates biomass-based sorbing material is placed in the water containing harmful anion adsorb.
Preferably, it is possible to biomass-based sorbing material is placed in the concussion of the water containing harmful anion or stirs, to accelerate absorption.
Preferably, described sorbing material is 0.01g/L-1g/L relative to the consumption containing harmful anion water; Concussion or churning time are 0.5-12 hour; Concussion or whipping temp are room temperature.
The useful effect of the present invention is as follows:
The biomass-based sorbing material of the present invention can have magnetic thus be easy to separation, has the free of contamination feature of environmental friendliness simultaneously.
The present invention take biological material as body material, contains the inorganic particle of iron and the inorganic particulate containing aluminium in described biomass-based surface load, utilizes the interaction between inorganic particulate and negatively charged ion to be adsorbed by harmful anion. Compared with harmful anion sorbing material of the prior art, the present invention adopts biomass agricultural wastes material to be binding matrix, and technique is simple, easy to operate, is applicable to the water pollutions process of multiple class harmful anion. Industrial scale is changeable, has both been conducive to promoting in remote rural area, personal user, has also been applicable to extensive water treatment.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates that the embodiment of the present invention 1 a kind of body material used rubs scanning electronic microscope (SEM) photo of the biological material powder that machining Wheat Straw obtains by machinery.
Fig. 2 illustrates scanning electronic microscope (SEM) photo of the sorbing material utilizing biological material to obtain that the embodiment of the present invention 4 is used for matrix carrying inorganic particle.
Fig. 3 illustrates the sorbing material of the embodiment of the present invention 5 photo under externally-applied magnetic field in water.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further. Parts similar in accompanying drawing represent with identical Reference numeral. It will be understood and appreciated by those or skill in the art that specifically described content is explanation property but not restrictive below, it should not limit the scope of the invention with this.
Embodiment 1
Adopt Wheat Straw to be the biological material powder (its electron scanning micrograph is as shown in Figure 1) obtained after Wheat Straw prepared by raw material rubs, prepare biological material/Fe3O4(sample 1), and sample 1 is carried out the test of absorption property.
In 100mL flask, add 50mL ultrapure water, 4.5gFeCl3��6H2O, 2.3gFeSO4��7H2O, 0.5g are rubbed by machinery and process the biological material powder that obtains, abundant dispersed with stirring, lead to into nitrogen 3 minutes, start to drip and add ammoniacal liquor, add ammoniacal liquor 10mL, continue logical nitrogen 2 minutes. After closed system, it is placed in 70 DEG C of oil bath reactions 4 hours, after termination reaction, reaction product is washed repeatedly, magnetic resolution, dry, obtain for the biomass-based sorbing material sample 1 except the middle harmful anion that anhydrates.
Get 0.05g sample 1, it is placed in 100mLAsO4 3-In solution, room temperature shakes 12 hours, measures with inductive coupling plasma emission spectrograph (instrument manufacturer facility man: ThermoFisher, INSTRUMENT MODEL: Thermo6300Series), inorganic particle due to iron content and the negatively charged ion generation complexing action containing arsenic, make AsO4 3-Concentration by adsorb front 0.074mg/L be reduced to absorption after 0.0098mg/L.
Inorganic particulate cost is lower, adsorption efficiency is relatively high, utilize biological material for matrix by inorganic particulate load biological material surface, be conducive to solve inorganic particulate due to mutually assemble thus make its specific surface area decline adsorption efficiency reduce shortcoming. Consider that single inorganic particulate is functional comparatively single, often better for the harmful anion absorption property of class a certain in water or a certain valency state, and the water body that reality need to process often has the harmful anion of the different multiple class of content, multivalent state, the sorbing material of the common load of multiple inorganic particulate on biomass matrix has the adsorptivity of wider scope, and the process for actual water body is more targeted. Considering cheapness, resource reutilization, as renewable resources the abundantest in nature and environment-friendly material, biological material is desirable adsorbent matrix material.
Therefore, the present invention is taking the biomass agricultural wastes material of cheapness as body material, utilize its surface containing a large amount of hydroxyls, these hydroxyls can be used for the growth load of adsorbing metal ions and then stable inorganic particle, load simultaneously the inorganic particle of iron and the inorganic particulate containing aluminium can be contained by original position co-precipitation, on biological material matrix, load has the inorganic particulate of negatively charged ion absorption property, prepares harmful anion sorbing material.
Embodiment 2
Adopt Wheat Straw to be the biological material powder obtained after Wheat Straw prepared by raw material rubs, prepare biological material/iron-aluminium (hydrogen) oxide compound (sample 2), and sample 2 is carried out the test of absorption property.
In 100mL flask, add 50mL ultrapure water, 4.5gFeCl3��6H2O, 2.3gFeSO4��7H2O, 9.4gAl (NO3)3��9H2O, 0.5g are rubbed by machinery and process the biological material powder that obtains, abundant dispersed with stirring, lead to into nitrogen 3 minutes, start to drip and add ammoniacal liquor, add ammoniacal liquor 20mL, continue logical nitrogen 2 minutes. After closed system, it is placed in 70 DEG C of oil bath reactions 4 hours, after termination reaction, reaction product is washed repeatedly, magnetic resolution, dry, obtain for the biomass-based sorbing material sample 2 except the middle harmful anion that anhydrates.
Get 0.1g sample 2, it is placed in 100mLF-In solution, stir 4 hours, measure fluorinion concentration with ionometer, owing to containing inorganic particulate and the F of aluminium-There is adsorption, make F-Concentration by adsorb front 3.99mg/L be reduced to absorption after 1.13mg/L.
Embodiment 3
Adopt Wheat Straw to be the biological material powder obtained after Wheat Straw prepared by raw material rubs, prepare biological material/iron-aluminium (hydrogen) oxide compound (sample 3), and sample 3 is carried out the test of absorption property.
In 100mL flask, add 50mL ultrapure water, 2.3gFeCl3��6H2O, 1.2gFeSO4��7H2O, 4.7gAl (NO3)3��9H2O, 0.5g are rubbed by machinery and process the biological material powder that obtains, abundant dispersed with stirring, lead to into nitrogen 3 minutes, start to drip and add ammoniacal liquor, add ammoniacal liquor 10mL, continue logical nitrogen 2 minutes. After closed system, it is placed in 70 DEG C of oil bath reactions 4 hours, after termination reaction, reaction product is washed repeatedly, separation, dry, obtain for the biomass-based sorbing material sample 3 except the middle harmful anion that anhydrates.
Get 0.1g sample 3, it is placed in 100mLF-In solution, stir 4 hours, measure fluorinion concentration with ionometer, owing to containing inorganic particulate and the F of aluminium-There is adsorption, make F-Concentration by adsorb front 3.99mg/L be reduced to absorption after 0.76mg/L.
Embodiment 4
Adopt Wheat Straw to be the biological material powder obtained after Wheat Straw prepared by raw material rubs, prepare biological material/iron-aluminium (hydrogen) oxide compound (sample 4), and sample 4 is carried out the test of absorption property.
In 100mL flask, add 50mL ultrapure water, 2.7gFeCl3��6H2O, 1.4gFeSO4��7H2O, 3.8gAl (NO3)3��9H2O, 0.5g are rubbed by machinery and process the biological material powder that obtains, abundant dispersed with stirring, lead to into nitrogen 3 minutes, start to drip and add ammoniacal liquor, add ammoniacal liquor 10mL, continue logical nitrogen 2 minutes. After closed system, it is placed in 70 DEG C of oil bath reactions 4 hours, after termination reaction, reaction product is washed repeatedly, separation, dry, obtaining for the biomass-based sorbing material sample 4 except the middle harmful anion that anhydrates, its scanning electronic microscope (SEM) photo is as shown in Figure 2.
Get 0.1g sample 4, it is placed in 100mLF-In solution, stir 4 hours, measure fluorinion concentration with ionometer, owing to containing inorganic particulate and the F of aluminium-There is adsorption, make F-Concentration by adsorb front 3.99mg/L be reduced to absorption after 0.64mg/L.
Embodiment 5
Adopt Wheat Straw to be the biological material powder obtained after Wheat Straw prepared by raw material rubs, prepare biological material/iron-aluminium (hydrogen) oxide compound (sample 5), and sample 5 is carried out the test of absorption property.
In 100mL flask, add 50mL ultrapure water, 3.6gFeCl3��6H2O, 1.9gFeSO4��7H2O, 1.9gAl (NO3)3��9H2O, 0.5g are rubbed by machinery and process the biological material powder that obtains, abundant dispersed with stirring, lead to into nitrogen 3 minutes, start to drip and add ammoniacal liquor, add ammoniacal liquor 10mL, continue logical nitrogen 2 minutes. After closed system, it is placed in 70 DEG C of oil bath reactions 4 hours, after termination reaction, reaction product is washed repeatedly, separation, drying, obtains for the biomass-based sorbing material sample 5 except the middle harmful anion that anhydrates, and it is the photo under externally-applied magnetic field in water, as shown in Figure 3: after adsorption process terminates, only needing an externally-applied magnetic field, sorbent material just can be separated with water easily and fast, can not remain and form secondary pollution in water.
Get 0.1g sample 5, it is placed in 100mLF-In solution, stir 4 hours, measure fluorinion concentration with ionometer, owing to containing inorganic particulate and the F of aluminium-There is adsorption, make F-Concentration by adsorb front 3.99mg/L be reduced to absorption after 1.35mg/L.
Embodiment 6
Adopt rice straw to be the biological material powder obtained after rice straw prepared by raw material rubs, prepare biological material/Fe3O4(sample 6), and sample 6 is carried out the test of absorption property.
In 100mL flask, add 50mL ultrapure water, 0.9gFeCl3��6H2O, 0.5gFeSO4��7H2O, 0.5g are rubbed by machinery and process the biological material powder that obtains, abundant dispersed with stirring, lead to into nitrogen 3 minutes, start to drip and add ammoniacal liquor, add ammoniacal liquor 2mL, continue logical nitrogen 2 minutes. After closed system, it is placed in 70 DEG C of oil bath reactions 4 hours, after termination reaction, reaction product is washed repeatedly, magnetic resolution, dry, obtain for the biomass-based sorbing material sample 6 except the middle harmful anion that anhydrates.
Get 0.1g sample 6, it is placed in 100mLAsO4 3-In solution, shaking 12 hours, with inductance coupled plasma optical emission spectrometer measurement, the inorganic particle due to iron content and the negatively charged ion generation complexing action containing arsenic, make AsO4 3-Concentration by adsorb front 0.237mg/L be reduced to absorption after 0.0062mg/L.
Embodiment 7
(1) by reed by mechanical disintegration, pulverizing into the powder of 100 ��m, the biological material powder obtained is as sorbing material matrix;
(2) when protection, the stirring of rare gas element, step (1) is obtained reed powder and containing Fe2+��Fe3+, and Al3+Water join in reactor, the amount of inorganic particulate and the ratio of biomass matrix are 0.5mol/g. React 24 hours at 20 DEG C, Fe in water2+Content is 0.025mol/L; Fe3+Content is 0.05mol/L; Al3+Content is 0.05mol/L; The add-on of ammoniacal liquor is 10mol/L
Ammoniacal liquor slowly adds above-mentioned reactor react; After reaction terminates, magnetic resolution reaction product, through washing, dry, obtain for the biomass-based sorbing material except the middle harmful anion that anhydrates.
Biomass-based sorbing material being placed in the water containing harmful anion stir, described sorbing material consumption is 1g/L, and the stirring at room temperature time is 12 hours, and gained result and embodiment 1 are close.
Embodiment 8
(1) by reed by mechanical disintegration, pulverizing into the powder of 100 ��m, the biological material powder obtained is as sorbing material matrix;
(2) when protection, the stirring of rare gas element, step (1) is obtained reed powder and containing Fe2+��Fe3+, and Al3+Water join in reactor, the amount of inorganic particulate and the ratio of biomass matrix are 0.005mol/g. React 1.5 hours at 100 DEG C, Fe in water2+Content is 0.5mol/L; Fe3+Content is 1.0mol/L; Al3+Content is 1.0mol/L; The add-on of ammoniacal liquor is 0.5mol/L.
Ammoniacal liquor slowly adds above-mentioned reactor react; After reaction terminates, magnetic resolution reaction product, through washing, dry, obtain for the biomass-based sorbing material except the middle harmful anion that anhydrates.
Biomass-based sorbing material being placed in the water containing harmful anion shake, sorbing material consumption is 0.01g/L, and 30 minutes stirring at room temperature time, gained result and embodiment 1 are close.
Embodiment 9-15
With embodiment 1, its difference is only: described raw material Wheat Straw is the grass bits on the awns bar of the quality such as use, bamboo, lawn, maize straw, soybean stalk, cotton stalk or sweet potato vine replacement respectively, and gained result and embodiment 1 are close.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and it is not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot giving exhaustive to all enforcement modes, the apparent change that the technical scheme of every the present invention of belonging to is extended out or variation are still in the row of protection scope of the present invention.
Claims (10)
1. one kind for the biomass-based sorbing material except the middle harmful anion that anhydrates, it is characterised in that: the area load inorganic particulate of described biomass-based sorbing material; The main raw material of described biomass-based sorbing material is agricultural wastes; Described harmful anion comprises F-, AsO2 -And AsO4 3-;
Described inorganic particulate is the inorganic particle containing iron and/or the inorganic particulate containing aluminium.
2. according to claim 1 for the biomass-based sorbing material except the middle harmful anion that anhydrates, it is characterised in that: the amount of described inorganic particulate and the ratio of biomass matrix are 0.005mol/g-0.5mol/g.
3. according to claim 1 for the biomass-based sorbing material except the middle harmful anion that anhydrates, it is characterised in that: the described inorganic particle containing iron is Fe3O4Inorganic particle; The described inorganic particulate containing aluminium is Al (OH)3Inorganic particulate.
4. according to claim 1 for the biomass-based sorbing material except the middle harmful anion that anhydrates, it is characterised in that: the raw material of described biomass-based sorbing material is selected from herbaceous plant or xylophyta.
5. according to claim 4 for the biomass-based sorbing material except the middle harmful anion that anhydrates, it is characterised in that: the mixing of one or more that described herbaceous plant is selected from the grass bits on agricultural crop straw, reed, reed reed, awns bar, bamboo or lawn; Described xylophyta is selected from fallen leaves or the wood chip of trees;
Preferably, the mixing of one or more that described agricultural crop straw is selected from wheat straw, straw, maize straw, soybean stalk, cotton stalk or sweet potato vine.
6. the preparation method for the biomass-based sorbing material except the middle harmful anion that anhydrates as described in claim 1-5 any one, it is characterised in that, comprise following preparation process:
(1) powder that the raw material powder of biomass-based sorbing material is broken into 100 ��m of-10mm, the biological material powder obtained is as sorbing material matrix;
(2) when protection of inert gas, stirring, step (1) is obtained biological material powder and containing Fe2+��Fe3+, and/or Al3+The aqueous solution join in reactor, under certain temperature, ammoniacal liquor is added above-mentioned reactor and reacts; After reaction terminates, magnetic resolution reaction product, through washing, dry, obtain for the biomass-based sorbing material except the middle harmful anion that anhydrates.
7. the preparation method for the biomass-based sorbing material except the middle harmful anion that anhydrates according to claim 6, it is characterised in that: described containing Fe2+��Fe3+, and/or Al3+The aqueous solution in Fe2+Content is 0.025mol/L-0.5mol/L; Fe3+Content is 0.05mol/L-1.0mol/L; Al3+Content is 0.05mol/L-1.0mol/L;
The concentration of described ammoniacal liquor is 25%, and ammoniacal liquor is 0.5mol/L-10mol/L relative to the add-on of the aqueous solution.
8. the preparation method for the biomass-based sorbing material except the middle harmful anion that anhydrates according to claim 7, it is characterized in that: the temperature of reaction described in step (2) is 20 DEG C-100 DEG C, step (2) the described reaction times is 1-24 hour.
9. the application for the biomass-based sorbing material except the middle harmful anion that anhydrates as described in claim 1-5 any one biomass-based sorbing material is placed in the water containing harmful anion adsorb.
10. the application for the biomass-based sorbing material except the middle harmful anion that anhydrates according to claim 9, it is characterised in that: described sorbing material is 0.01g/L-1g/L relative to the consumption containing harmful anion water; Described adsorption time is 0.5-12 hour; Adsorption temp is room temperature.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106799205A (en) * | 2016-12-22 | 2017-06-06 | 新疆水处理工程技术研究中心有限公司 | A kind of preparation method of drinking water fluorine removal arsenic adsorbent |
| CN107986374A (en) * | 2017-11-29 | 2018-05-04 | 北京科技大学 | The method of biological adsorption material and fluorine in polymer matrix composites cooperation-removal water |
| CN110538639A (en) * | 2019-09-24 | 2019-12-06 | 信阳学院 | Preparation and application of high-purity magnetic peanut shell biomass adsorbing material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139202A (en) * | 2010-01-28 | 2011-08-03 | 中国科学院理化技术研究所 | Cellulose-based adsorption material for removing arsenic and fluorine ions in water and preparation method thereof |
| CN102476043A (en) * | 2010-11-26 | 2012-05-30 | 中国科学院理化技术研究所 | Cellulose base/Fe for arsenic removal in water3O4Composite adsorption material and preparation method thereof |
| CN103495389A (en) * | 2013-08-30 | 2014-01-08 | 蚌埠凤凰滤清器有限责任公司 | Modified straw activated carbon water treatment agent and its preparation method |
| EP2703362A2 (en) * | 2009-07-08 | 2014-03-05 | Saudi Arabian Oil Company | Low concentration wastewater treatment system and process |
-
2014
- 2014-11-15 CN CN201410648617.4A patent/CN105642241A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2703362A2 (en) * | 2009-07-08 | 2014-03-05 | Saudi Arabian Oil Company | Low concentration wastewater treatment system and process |
| CN102139202A (en) * | 2010-01-28 | 2011-08-03 | 中国科学院理化技术研究所 | Cellulose-based adsorption material for removing arsenic and fluorine ions in water and preparation method thereof |
| CN102476043A (en) * | 2010-11-26 | 2012-05-30 | 中国科学院理化技术研究所 | Cellulose base/Fe for arsenic removal in water3O4Composite adsorption material and preparation method thereof |
| CN103495389A (en) * | 2013-08-30 | 2014-01-08 | 蚌埠凤凰滤清器有限责任公司 | Modified straw activated carbon water treatment agent and its preparation method |
Non-Patent Citations (6)
| Title |
|---|
| XIAOLI ZHAO ET AL: "Removal of fluoride from aqueous media by Fe3O4@Al(OH)3 magnetic nanoparticles", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| YE TIAN ET AL: "Synthesis of magnetic wheat straw for arsenic adsorption", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 刘峥等: "《有机化学实验绿色化教程》", 31 January 2010, 冶金工业出版社 * |
| 曾林泉等: "《染整试化验及成品检测400问》", 28 February 2014, 中国纺织出版社 * |
| 杨天明等: "铁铝复合氧化物吸附砷氟性能实验研究", 《广东化工》 * |
| 梁美娜等: "氢氧化铝对砷的吸附作用", 《桂林工学院学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106799205A (en) * | 2016-12-22 | 2017-06-06 | 新疆水处理工程技术研究中心有限公司 | A kind of preparation method of drinking water fluorine removal arsenic adsorbent |
| CN107986374A (en) * | 2017-11-29 | 2018-05-04 | 北京科技大学 | The method of biological adsorption material and fluorine in polymer matrix composites cooperation-removal water |
| CN110538639A (en) * | 2019-09-24 | 2019-12-06 | 信阳学院 | Preparation and application of high-purity magnetic peanut shell biomass adsorbing material |
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