CN106622099A - Preparation method of arsenic adsorbing material and renaturation reuse method thereof - Google Patents

Preparation method of arsenic adsorbing material and renaturation reuse method thereof Download PDF

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CN106622099A
CN106622099A CN201610587425.6A CN201610587425A CN106622099A CN 106622099 A CN106622099 A CN 106622099A CN 201610587425 A CN201610587425 A CN 201610587425A CN 106622099 A CN106622099 A CN 106622099A
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arsenic
culture
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dlc
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CN106622099B (en
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陈朋
王宁波
王青
王一青
李素岳
路广通
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Lanzhou University
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0281Sulfates of compounds other than those provided for in B01J20/045
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/048Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/345Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents

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Abstract

The invention relates a preparation method of an arsenic adsorbing material. The method includes steps of (1), preparing a seed culture medium; (2), preparing a biotransformation culture medium; (3), preparing a standby solid; (4), preparing a soft agarose culture medium; (5), mixing eosino-ferrous oxide thiobacillus DLC-5 bacteria solution with soft agarose culture medium, condensing at constant temperature to obtain ferrous oxide thiobacillus DLC-5 culture; (6), activating culture: inoculating the ferrous oxide thiobacillus DLC-5 culture to a shake flask having a seed culture medium to perform shake cultivation to obtain the culture activating fluid; (7), biotransformation: inoculating the culture activating fluid to the shake flask with the biotransformation culture medium to obtain the culture fluid; (8), adding standby solid in the culture fluid, and then stirring and performing the ultrasound treatment to obtain the colloidal solution; (9), pouring colloidal solution in the absolute ethyl alcohol, and acquiring a flocculent; drying and grinding the flocculent to obtain the arsenic adsorbing material. The invention further discloses a renaturation reuse method of the arsenic adsorbing material. The invention is fast, simple and environment-friendly.

Description

A kind of preparation of arsenic adsorbent material and its renaturation reuse method
Technical field
The present invention relates to environmental science, more particularly to a kind of preparation and its renaturation reuse method of arsenic adsorbent material.
Background technology
Show severity special graceful stone, its chemical formula is represented by Fe8O8(OH)8-2x(SO4)x, it is a kind of poor secondary light of degree of crystallinity The high iron mineral of base sulfate.The mineral formation is closely related with the effect of acidophil, while numerous studies show, special graceful stone of showing severity Counterweight (class) metal ion has absorption and co-precipitation, and some toxic elements can be promoted to be passivated naturally.Show severity special graceful stone structure Interior SO4 2-It is to be complexed with two tooth double-core forms and Fe coordination shells, while mineral surfaces are adsorbed with rising to its structure in a large number The SO of stabilization4 2-, therefore the anion higher with Fe coordination abilities, such as:AsO4 3-, may replace SO4 2-.Show severity special graceful stone this Plant characteristic so as to which environmental science has important application prospect.
Extreme acidophilic microorganism present in nature --- Acidithiobacillus ferrooxidans strain GF (Acidithiobacillus ferrooxidans) closely related with the microbiological oxidation of pyrite, special graceful stone of showing severity is one of metabolite of the bacterium. By microbe transformation method, can obtain that high-specific surface area, mesoporous construction, particle be homogeneous, good dispersion special graceful stone material of showing severity Material.The method for preparing new material and biological renaturation using bioanalysis simultaneously is regenerated, safe with environmental friendliness, nothing Secondary pollution, low cost and other advantages become a kind of arsenic-containing water treatment technology with very big application potential.
The content of the invention
The technical problem to be solved is to provide a kind of quick, easy, environmental protection arsenic adsorbent material preparation.
Another technical problem to be solved by this invention is to provide the renaturation reuse method of the arsenic adsorbent material.
To solve the above problems, a kind of preparation method of arsenic adsorbent material of the present invention is comprised the following steps:
(1) a liquid and b liquid are pressed into 7:3 volume ratio mixing, obtains final product seed culture medium;Wherein
The a liquid is referred to ammonium sulfate 3.00g, potassium chloride 0.10g, dipotassium hydrogen phosphate 0.50g, magnesium sulfate 0.50g, calcium nitrate 0.01g is dissolved in 700mL distilled water, and adjusts the solution of pH value to 1.5 ~ 1.9 gained with the concentrated sulfuric acid;
The b liquid refers to that ferrous sulfate 44.70g is dissolved in the solution of gained in 300mL distilled water;
(2) A liquid and B liquid are pressed into 7:3 volume ratio mixing, obtains final product biotransformation medium;Wherein
The A liquid refer to ammonium sulfate 3.00g, 0.10 ~ 0.20g of potassium chloride, 0.50 ~ 1.00g of dipotassium hydrogen phosphate, magnesium sulfate 0.50g, Calcium nitrate 0.01g is dissolved in 700mL distilled water, and 0.20 ~ 5.00g shells are added to after 1.9 ~ 2.9 with concentrated sulfuric acid adjustment pH value Glycan stirring makes the solution obtained by its dissolving;
The B liquid refers to that 50.00 ~ 100.00g of ferrous sulfate is dissolved in the solution of gained in 300mL distilled water;
(3) by 0.10 ~ 2.00g nanometers ZrO2After mixing with 0.10 ~ 3.00g neopelexes, 100mL deionizations are added Water, after stirring 4 ~ 8h at 20 ~ 40 DEG C, is precipitated thing, and the sediment is dried Jing after washes of absolute alcohol at 50 ~ 60 DEG C, Obtain final product standby solid;
(4) 100mL distilled water is added in 1.00 ~ 2.00g agaroses, and boiling dissolves it, when being cooled to 50 ~ 60 DEG C, obtains final product Soft agarose culture medium;
(5) the stationary phase Acidithiobacillus ferrooxidans strain GF DLC-5 that will be preserved at 0 DEG C(Acidithiobacillus ferrooxidans DLC-5)Bacterium solution presses 7:3 volume ratio mixes with the soft agarose culture medium, and air-setting obtains final product oxygen Change ferrous Thiobacillus DLC-5 bacterial classifications, the Thiobacillus ferrooxidans DLC-5 fungi preservations are at 2 ~ 4 DEG C;
The Acidithiobacillus ferrooxidans strain GF DLC-5 is CCTCC NO in the deposit number of China typical culture collection center:M 2014362(Depositary institution address:China. Wuhan. Wuhan University;Preservation date:On 07 28th, 2014);
(6) actication of culture:The Thiobacillus ferrooxidans DLC-5 bacterial classifications are seeded to equipped with containing described by 8 ~ 12% inoculum concentration In the shaking flask of seed culture medium, it is placed on constant temperature oscillator, is entered with the speed of 100 ~ 200 r/min under the conditions of 25 ~ 35 DEG C Row 60 ~ 84h of shaken cultivation, obtains final product actication of culture liquid;Bottling amount of the seed culture medium in the shaking flask is 40 ~ 60%;
(7) bioconversion:The actication of culture liquid is seeded to containing the biotransformation medium by 15 ~ 25% inoculum concentration In shaking flask, be placed on constant temperature oscillator, under the conditions of 25 ~ 35 DEG C with the speed of 100 ~ 200 r/min carry out shaken cultivation 30 ~ 50h, obtains final product nutrient solution;Bottling amount of the biotransformation medium in the shaking flask is 40 ~ 60%;
(8) the standby solid added in the nutrient solution, after gained mixture stirs 1 ~ 2h at 25 ~ 35 DEG C, at Jing is ultrasonic 10 ~ 20min of reason, obtains final product the colloidal solution of high dispersive;
(9) during the colloidal solution to be poured into the absolute ethyl alcohol of 1 ~ 4 times of its volume, flocculent deposit is obtained;The flocculent deposit spends Ionized water replace with absolute ethyl alcohol cleaning to filtrate it is colourless after, temperature be 60 ~ 80 DEG C under conditions of be dried under vacuum to constant weight, and It is 150 ~ 200 mesh to be ground to fineness, obtains final product arsenic adsorbent material.
The renaturation reuse method of the arsenic adsorbent material that a kind of preparation method of arsenic adsorbent material as above is obtained, its It is characterised by:The arsenic adsorbent material is filled to adsorption column as packing material, the aqueous sulfuric acid wash-out of 0.01 ~ 0.2M of Jing Afterwards, renaturation is carried out using the actication of culture liquid.
The application of the arsenic adsorbent material that a kind of preparation method of arsenic adsorbent material as above is obtained, its feature exists In:The arsenic adsorbent material is filled to adsorption column as packing material, and pH value is carried out at arsenic for 7 ~ 10 sewage containing arsenic ion Reason;One or more referred to containing arsenic ion in arsenite ion, arsenic acid ion, arsenic anhydride.
The present invention has compared with prior art advantages below:
1st, the present invention replaces chemical method using biotransformation method, efficiently solves the specific surface area that chemical method prepares special graceful stone of showing severity Little, particle is big, and the shortcomings of adsorption effect is not good, arsenic adsorption rate can reach more than 90%.
2nd, the present invention adopts biological desorption, by sorbing material renaturation, while reclaiming metal.
3rd, present invention preparation is convenient, simple and direct, with higher biological safety, to special graceful stone of showing severity in sewage treatment area Widely application provides the foundation.
Specific embodiment
A kind of preparation method of the arsenic adsorbent material of embodiment 1, comprises the following steps:
(1) a liquid and b liquid are pressed into 7mL:The volume ratio mixing of 3mL, obtains final product seed culture medium.Wherein
A liquid is referred to ammonium sulfate 3.00g, potassium chloride 0.10g, dipotassium hydrogen phosphate 0.50g, magnesium sulfate 0.50g, calcium nitrate 0.01g In being dissolved in 700mL distilled water, and the solution of pH value to 1.7 gained is adjusted with the concentrated sulfuric acid;
B liquid refers to that ferrous sulfate 44.70g is dissolved in the solution of gained in 300mL distilled water.
(2) A liquid and B liquid are pressed into 7mL:The volume ratio mixing of 3mL, obtains final product biotransformation medium.Wherein
A liquid refers to that ammonium sulfate 3.00g, potassium chloride 0.10g, dipotassium hydrogen phosphate 0.50g, magnesium sulfate 0.50g, calcium nitrate 0.01g are molten Solution adds the stirring of 0.70g shitosans to make obtained by its dissolving with concentrated sulfuric acid adjustment pH value in 700mL distilled water to after 2.5 Solution;
B liquid refers to that ferrous sulfate 56.00g is dissolved in the solution of gained in 300mL distilled water.
(3) by 0.17g nanometers ZrO2After mixing with 0.53g neopelexes, 100mL deionized waters are added, 40 Stir after 4h at DEG C, be precipitated thing, the sediment is dried Jing after washes of absolute alcohol at 60 DEG C, obtains final product standby solid.
(4) 100mL distilled water is added in 2.00g agaroses, and boiling dissolves it, when being cooled to 60 DEG C, obtains final product soft fine jade Lipolysaccharide culture medium.
(5) the stationary phase Acidithiobacillus ferrooxidans strain GF DLC-5 that will be preserved at 0 DEG C(Acidithiobacillus ferrooxidans DLC-5;Deposit numbers of the Acidithiobacillus ferrooxidans strain GF DLC-5 in China typical culture collection center For CCTCC NO:M 2014362, depositary institution address:China. Wuhan. Wuhan University;Preservation date:On 07 28th, 2014) Bacterium solution presses 7mL:The volume ratio of 3mL mixes with soft agarose culture medium, air-setting, obtains final product Thiobacillus ferrooxidans DLC-5 bacterium Kind, the Thiobacillus ferrooxidans DLC-5 fungi preservations are at 2 ~ 4 DEG C.
(6) actication of culture:Thiobacillus ferrooxidans DLC-5 bacterial classifications are seeded to equipped with containing seed training by 10% inoculum concentration In the shaking flask of foster base, it is placed on constant temperature oscillator, shaken cultivation 72h is carried out with the speed of 100 r/min under the conditions of 25 DEG C, Obtain final product actication of culture liquid;Bottling amount of the seed culture medium in shaking flask is 60%.
(7) bioconversion:Actication of culture liquid is seeded in the shaking flask containing biotransformation medium by 20% inoculum concentration, It is placed on constant temperature oscillator, shaken cultivation 40h is carried out with the speed of 150 r/min under the conditions of 25 DEG C, obtains final product nutrient solution;It is raw It is 40% that thing converts bottling amount of the culture medium in shaking flask.
(8) after adding standby solid, gained mixture to stir 1h at 25 DEG C in nutrient solution, sonicated 10min, Obtain final product the colloidal solution of high dispersive.
(9) during colloidal solution to be poured into the absolute ethyl alcohol of 2 times of its volume, flocculent deposit is obtained;Flocculent deposit deionized water Replace with absolute ethyl alcohol cleaning to filtrate it is colourless after, be to be dried under vacuum to constant weight under conditions of 70 DEG C in temperature, and be ground to thin Spend for 180 mesh, obtain final product arsenic adsorbent material.
A kind of preparation method of the arsenic adsorbent material of embodiment 2, comprises the following steps:
(1) a liquid and b liquid are pressed into 7mL:The volume ratio mixing of 3mL, obtains final product seed culture medium.Wherein
A liquid is referred to ammonium sulfate 3.00g, potassium chloride 0.10g, dipotassium hydrogen phosphate 0.50g, magnesium sulfate 0.50g, calcium nitrate 0.01g In being dissolved in 700mL distilled water, and the solution of pH value to 1.5 gained is adjusted with the concentrated sulfuric acid;
B liquid refers to that ferrous sulfate 44.70g is dissolved in the solution of gained in 300mL distilled water.
(2) A liquid and B liquid are pressed into 7mL:The volume ratio mixing of 3mL, obtains final product biotransformation medium.Wherein
A liquid refers to that ammonium sulfate 3.00g, potassium chloride 0.15g, dipotassium hydrogen phosphate 0.80g, magnesium sulfate 0.50g, calcium nitrate 0.01g are molten Solution adds the stirring of 0.20g shitosans to make obtained by its dissolving with concentrated sulfuric acid adjustment pH value in 700mL distilled water to after 1.9 Solution;
B liquid refers to that ferrous sulfate 50.00g is dissolved in the solution of gained in 300mL distilled water.
(3) by 0.10g nanometers ZrO2After mixing with 0.10g neopelexes, 100mL deionized waters are added, 20 Stir after 8h at DEG C, be precipitated thing, the sediment is dried Jing after washes of absolute alcohol at 50 DEG C, obtains final product standby solid.
(4) 100mL distilled water is added in 1.00g agaroses, and boiling dissolves it, when being cooled to 50 DEG C, obtains final product soft fine jade Lipolysaccharide culture medium.
(5) the stationary phase Acidithiobacillus ferrooxidans strain GF DLC-5 that will be preserved at 0 DEG C(Acidithiobacillus ferrooxidans DLC-5;Deposit numbers of the Acidithiobacillus ferrooxidans strain GF DLC-5 in China typical culture collection center For CCTCC NO:M 2014362, depositary institution address:China. Wuhan. Wuhan University;Preservation date:On 07 28th, 2014) Bacterium solution presses 7mL:The volume ratio of 3mL mixes with soft agarose culture medium, air-setting, obtains final product Thiobacillus ferrooxidans DLC-5 bacterium Kind, the Thiobacillus ferrooxidans DLC-5 fungi preservations are at 2 ~ 4 DEG C.
(6) actication of culture:Thiobacillus ferrooxidans DLC-5 bacterial classifications are seeded to equipped with containing seed training by 8% inoculum concentration In the shaking flask of foster base, it is placed on constant temperature oscillator, shaken cultivation 60h is carried out with the speed of 150 r/min under the conditions of 30 DEG C, Obtain final product actication of culture liquid;Bottling amount of the seed culture medium in shaking flask is 40%.
(7) bioconversion:Actication of culture liquid is seeded in the shaking flask containing biotransformation medium by 15% inoculum concentration, It is placed on constant temperature oscillator, shaken cultivation 30h is carried out with the speed of 100 r/min under the conditions of 30 DEG C, obtains final product nutrient solution;It is raw It is 50% that thing converts bottling amount of the culture medium in shaking flask.
(8) it is sonicated after adding standby solid, gained mixture to stir 1.5h at 30 DEG C in nutrient solution 15min, obtains final product the colloidal solution of high dispersive.
(9) during colloidal solution to be poured into the absolute ethyl alcohol of 1 times of its volume, flocculent deposit is obtained;Flocculent deposit deionized water Replace with absolute ethyl alcohol cleaning to filtrate it is colourless after, be to be dried under vacuum to constant weight under conditions of 60 DEG C in temperature, and be ground to thin Spend for 150 mesh, obtain final product arsenic adsorbent material.
A kind of preparation method of the arsenic adsorbent material of embodiment 3, comprises the following steps:
(1) a liquid and b liquid are pressed into 7mL:The volume ratio mixing of 3mL, obtains final product seed culture medium.Wherein
A liquid is referred to ammonium sulfate 3.00g, potassium chloride 0.10g, dipotassium hydrogen phosphate 0.50g, magnesium sulfate 0.50g, calcium nitrate 0.01g In being dissolved in 700mL distilled water, and the solution of pH value to 1.9 gained is adjusted with the concentrated sulfuric acid;
B liquid refers to that ferrous sulfate 44.70g is dissolved in the solution of gained in 300mL distilled water.
(2) A liquid and B liquid are pressed into 7mL:The volume ratio mixing of 3mL, obtains final product biotransformation medium.Wherein
A liquid refers to that ammonium sulfate 3.00g, potassium chloride 0.20g, dipotassium hydrogen phosphate 1.00g, magnesium sulfate 0.50g, calcium nitrate 0.01g are molten Solution adds the stirring of 5.00g shitosans to make obtained by its dissolving with concentrated sulfuric acid adjustment pH value in 700mL distilled water to after 2.9 Solution;
B liquid refers to that ferrous sulfate 100.00g is dissolved in the solution of gained in 300mL distilled water.
(3) by 2.00g nanometers ZrO2After mixing with 3.00g neopelexes, 100mL deionized waters are added, 30 Stir after 6h at DEG C, be precipitated thing, the sediment is dried Jing after washes of absolute alcohol at 55 DEG C, obtains final product standby solid.
(4) 100mL distilled water is added in 1.50g agaroses, and boiling dissolves it, when being cooled to 55 DEG C, obtains final product soft fine jade Lipolysaccharide culture medium.
(5) the stationary phase Acidithiobacillus ferrooxidans strain GF DLC-5 that will be preserved at 0 DEG C(Acidithiobacillus ferrooxidans DLC-5;Deposit numbers of the Acidithiobacillus ferrooxidans strain GF DLC-5 in China typical culture collection center For CCTCC NO:M 2014362, depositary institution address:China. Wuhan. Wuhan University;Preservation date:On 07 28th, 2014) Bacterium solution presses 7mL:The volume ratio of 3mL mixes with soft agarose culture medium, air-setting, obtains final product Thiobacillus ferrooxidans DLC-5 bacterium Kind, the Thiobacillus ferrooxidans DLC-5 fungi preservations are at 2 ~ 4 DEG C.
(6) actication of culture:Thiobacillus ferrooxidans DLC-5 bacterial classifications are seeded to equipped with containing seed training by 12% inoculum concentration In the shaking flask of foster base, it is placed on constant temperature oscillator, shaken cultivation 84h is carried out with the speed of 200 r/min under the conditions of 35 DEG C, Obtain final product actication of culture liquid;Bottling amount of the seed culture medium in shaking flask is 50%.
(7) bioconversion:Actication of culture liquid is seeded in the shaking flask containing biotransformation medium by 25% inoculum concentration, It is placed on constant temperature oscillator, shaken cultivation 50h is carried out with the speed of 200 r/min under the conditions of 35 DEG C, obtains final product nutrient solution;It is raw It is 60% that thing converts bottling amount of the culture medium in shaking flask.
(8) after adding standby solid, gained mixture to stir 2h at 35 DEG C in nutrient solution, sonicated 20min, Obtain final product the colloidal solution of high dispersive.
(9) during colloidal solution to be poured into the absolute ethyl alcohol of 4 times of its volume, flocculent deposit is obtained;Flocculent deposit deionized water Replace with absolute ethyl alcohol cleaning to filtrate it is colourless after, be to be dried under vacuum to constant weight under conditions of 80 DEG C in temperature, and be ground to thin Spend for 200 mesh, obtain final product arsenic adsorbent material.
The renaturation reuse method of the arsenic adsorbent material obtained in above-described embodiment 1 ~ 3 is referred to:The arsenic adsorbent material conduct Packing material is filled to adsorption column, Jing after the aqueous sulfuric acid wash-out of 0.01 ~ 0.2M, renaturation is carried out i.e. using actication of culture liquid Can.
The application of the arsenic adsorbent material obtained in above-described embodiment 1 ~ 3 is referred to:The arsenic adsorbent material is used as packing material Fill to adsorption column, arsenic process is carried out for 7 ~ 10 sewage containing arsenic ion to pH value;Arsenite ion, arsenic are referred to containing arsenic ion One or more in acid ion, arsenic anhydride.

Claims (3)

1. a kind of preparation method of arsenic adsorbent material, comprises the following steps:
(1) a liquid and b liquid are pressed into 7:3 volume ratio mixing, obtains final product seed culture medium;Wherein
The a liquid is referred to ammonium sulfate 3.00g, potassium chloride 0.10g, dipotassium hydrogen phosphate 0.50g, magnesium sulfate 0.50g, calcium nitrate 0.01g is dissolved in 700mL distilled water, and adjusts the solution of pH value to 1.5 ~ 1.9 gained with the concentrated sulfuric acid;
The b liquid refers to that ferrous sulfate 44.70g is dissolved in the solution of gained in 300mL distilled water;
(2) A liquid and B liquid are pressed into 7:3 volume ratio mixing, obtains final product biotransformation medium;Wherein
The A liquid refer to ammonium sulfate 3.00g, 0.10 ~ 0.20g of potassium chloride, 0.50 ~ 1.00g of dipotassium hydrogen phosphate, magnesium sulfate 0.50g, Calcium nitrate 0.01g is dissolved in 700mL distilled water, and 0.20 ~ 5.00g shells are added to after 1.9 ~ 2.9 with concentrated sulfuric acid adjustment pH value Glycan stirring makes the solution obtained by its dissolving;
The B liquid refers to that 50.00 ~ 100.00g of ferrous sulfate is dissolved in the solution of gained in 300mL distilled water;
(3) by 0.10 ~ 2.00g nanometers ZrO2After mixing with 0.10 ~ 3.00g neopelexes, 100mL deionizations are added Water, after stirring 4 ~ 8h at 20 ~ 40 DEG C, is precipitated thing, and the sediment is dried Jing after washes of absolute alcohol at 50 ~ 60 DEG C, Obtain final product standby solid;
(4) 100mL distilled water is added in 1.00 ~ 2.00g agaroses, and boiling dissolves it, when being cooled to 50 ~ 60 DEG C, obtains final product Soft agarose culture medium;
(5) the stationary phase Acidithiobacillus ferrooxidans strain GF DLC-5 that will be preserved at 0 DEG C(Acidithiobacillus ferrooxidans DLC-5)Bacterium solution presses 7:3 volume ratio mixes with the soft agarose culture medium, and air-setting obtains final product oxygen Change ferrous Thiobacillus DLC-5 bacterial classifications, the Thiobacillus ferrooxidans DLC-5 fungi preservations are at 2 ~ 4 DEG C;
The Acidithiobacillus ferrooxidans strain GF DLC-5 is CCTCC NO in the deposit number of China typical culture collection center:M 2014362;
(6) actication of culture:The Thiobacillus ferrooxidans DLC-5 bacterial classifications are seeded to equipped with containing described by 8 ~ 12% inoculum concentration In the shaking flask of seed culture medium, it is placed on constant temperature oscillator, is entered with the speed of 100 ~ 200 r/min under the conditions of 25 ~ 35 DEG C Row 60 ~ 84h of shaken cultivation, obtains final product actication of culture liquid;Bottling amount of the seed culture medium in the shaking flask is 40 ~ 60%;
(7) bioconversion:The actication of culture liquid is seeded to containing the biotransformation medium by 15 ~ 25% inoculum concentration In shaking flask, be placed on constant temperature oscillator, under the conditions of 25 ~ 35 DEG C with the speed of 100 ~ 200 r/min carry out shaken cultivation 30 ~ 50h, obtains final product nutrient solution;Bottling amount of the biotransformation medium in the shaking flask is 40 ~ 60%;
(8) the standby solid added in the nutrient solution, after gained mixture stirs 1 ~ 2h at 25 ~ 35 DEG C, at Jing is ultrasonic 10 ~ 20min of reason, obtains final product the colloidal solution of high dispersive;
(9) during the colloidal solution to be poured into the absolute ethyl alcohol of 1 ~ 4 times of its volume, flocculent deposit is obtained;The flocculent deposit spends Ionized water replace with absolute ethyl alcohol cleaning to filtrate it is colourless after, temperature be 60 ~ 80 DEG C under conditions of be dried under vacuum to constant weight, and It is 150 ~ 200 mesh to be ground to fineness, obtains final product arsenic adsorbent material.
2. the renaturation reuse side of the arsenic adsorbent material that a kind of preparation method of arsenic adsorbent material as claimed in claim 1 is obtained Method, it is characterised in that:The arsenic adsorbent material is filled to adsorption column as packing material, the aqueous sulfuric acid of 0.01 ~ 0.2M of Jing After wash-out, renaturation is carried out using the actication of culture liquid.
3. the application of the arsenic adsorbent material that a kind of preparation method of arsenic adsorbent material as claimed in claim 1 is obtained, it is special Levy and be:The arsenic adsorbent material is filled to adsorption column as packing material, and pH value is carried out for 7 ~ 10 sewage containing arsenic ion Arsenic process;One or more referred to containing arsenic ion in arsenite ion, arsenic acid ion, arsenic anhydride.
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