CN104445827A - Method for synthesizing jarosite to process pickling waste water employing biological method - Google Patents
Method for synthesizing jarosite to process pickling waste water employing biological method Download PDFInfo
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- CN104445827A CN104445827A CN201410766052.XA CN201410766052A CN104445827A CN 104445827 A CN104445827 A CN 104445827A CN 201410766052 A CN201410766052 A CN 201410766052A CN 104445827 A CN104445827 A CN 104445827A
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- pickling waste
- jarosite
- waste waters
- ferrivorans
- waste water
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Abstract
The invention discloses a method for synthesizing jarosite to process pickling waste water employing a biological method. According to the method, aiming at heavy metal ions (Cr<3+> and Ni<2+>) in the pickling waste water, the jarosite is synthesized by taking Fe<2+> in the pickling waste water as an energy source employing the biological method; and meanwhile, heavy metal ions in the pickling waste water are removed and filtered, so as to obtain jarosite and the pickling waste water free of heavy metal ions. The method comprises the following specific steps: with acidophilic thiobacillus A.ferrivorans as experimental bacteria, and the pickling waste water as a solution, preparing 9K of culture medium; adding 150ml of culture medium to a 250ml of conical flask, adding an energy source substance Fe<2+>, feeding 1ml of A.ferrivorans bacterium liquid, and controlling the initial pH to be 1.5-3.5, the initial concentration of Fe<2+> to be 0.5-10g/L, and the temperature to be 15-35 DEG C; and reacting in a 180r/min of constant-temperature oscillation box for 8-10 days, wherein at most 3.17g of jarosite can be synthesized; and the removal rate of the heavy metal ions Cr<3+> and Ni<2+> can be up to 87.02% and 55.30%.
Description
Technical field
The present invention relates to a kind for the treatment of process of pickling waste waters, be specifically related to the method for a kind of biological process synthesis jarosite process pickling waste waters.
Background technology
In the process of manufacture of steel industry, the courses of processing such as inevitably annealed, normalizing, quenching, welding, surface can produce the oxide skin of black often.Oxide skin not only affects the visual appearance of steel, also can have a negative impact to the following process of product, therefore the surface treatment such as pickling, polishing granting must be adopted before following process to be gone out.Acid cleaning process mainly cleans product with nitration mixture such as hydrochloric acid or sulfuric acid, hydrofluoric acid and nitric acid.But a large amount of pickling waste waterss can be produced in acid cleaning process.
Containing a large amount of Fe in pickling waste waters
2+and Fe
3+, simultaneously containing a large amount of heavy metal ion, particularly Cr
3+, Ni
2+content is the highest, huge to harm.The process of China's present stage pickling waste waters is use the simplest precipitator method substantially, although simple to operate, iron ions a large amount of in waste water can not get recycling, and wastes a large amount of useful resources.The method of current process pickling waste waters has:
Chinese patent 1 (CN 201010613021.2) discloses the treatment process of a kind of Iron And Steel Industry pickling waste waters and metal ion, and the method adopts feeding lime neutralization precipitation heavy-metal ion removal, and carries out solid-liquid separation with membrane separation apparatus.
Chinese patent 2 (CN 201210491599.4) discloses a kind for the treatment of process of industrial acid-washed waste water, and the method adopts pickling waste waters synthetic hydrotalcite, removes the heavy metal ion in waste water.
There is following defect in the treatment process of above-mentioned pickling waste waters:
(1) described method needs to add the medicaments such as a large amount of lime and alkali lye, generates a large amount of precipitations simultaneously.Precipitation is called pickling mud, also has a large amount of heavy metal ion, belongs to Hazardous wastes (HW17), cause secondary pollution, as patent 1.
(2) described method needs to add appropriate trivalent or divalent-metal ion to regulate the ratio of ion, and increase cost, the wasting of resources, as patent 2.
Summary of the invention
The object of the invention is to for the heavy metal ion (Cr in pickling waste waters
3+, Ni
2+), employing acidophilic thiobacillus A.ferrivoran utilizes the Fe in pickling waste waters
2+for energy organism method synthesis jarosite, remove heavy metal ion wherein simultaneously, provide a kind of biological process to synthesize the method for jarosite process pickling waste waters.
The technical solution realizing the object of the invention is: a kind of method of biological process synthesis jarosite process pickling waste waters, comprises the steps:
(1) separation and purification A.ferrivorans: get second pond mud from sewage work, obtains the A.ferrivorans of pure culture after separation and purification;
(2) pickling waste waters pre-treatment: after being filtered by pickling waste waters, sterilizing is for subsequent use;
(3) synthesis of jarosite and the removal of heavy metal: with the pickling waste waters after sterilizing for solution preparation 9K substratum, add the A.ferrivorans bacterium liquid of pure culture, acid adding regulates initial pH, adds ferrous ion salt and regulates initial Fe
2+concentration, shaking table reacts, and after reaction terminates, generates precipitation as jarosite, removes the heavy metal ion in pickling waste waters simultaneously.
In described step (1), separation and purification refers to preparation 9K substratum and adds FeSO
47H
2o, carries out the Secondary Culture of three to four times by mud, adopt double-layer agar technique coating, purifying obtains the A.ferrivorans bacterium liquid of pure culture.
The 0.22 μm of membrane filtration sterilizing of pickling waste waters in described step (2).
Initial pH in described step (3) controls 1.5 ~ 3.5, adds initial Fe
2+concentration control at 0.5 ~ 10g/L, ferrous ion salt adopt FeSO
47H
2o, reaction process temperature controls at 15 ~ 35 DEG C, and shaking speed is at 180r/min, and the reaction times is 8 ~ 10 days.
Principle illustrates:
Acidophilic thiobacillus A.ferrivorans growth process in, Fe in solution
2+constantly be oxidized to Fe
3+, and Fe
3+, there is a series of hydrolysis reaction in facile hydrolysis, forms multiple multinuclear hydroxyl complex ion, and these multinuclear hydroxyl complex ions assemble growth using the thalline in solution as nucleation site, and the final jarosite class that formed precipitates.
Jarosite [KFe
3(SO
4)
2(OH)
6] be the ochre yellow mineral dye of excellent performance, rare costliness, biological process synthesis jarosite is short without the need to High Temperature High Pressure, time, and due to the effect of microorganism extracellular polymeric, that synthesizes than chemical process has better homogeneity and more perfect crystal formation, therefore in materials application, has higher potentiality.Simultaneously because the jarosite of new life has specific surface area greatly, some coexisting ion in energy strong adsorption solution, thus play the effect of removing some impurity or some valuable metal of enrichment in solution.
Compared with prior art, its remarkable advantage is in the present invention:
(1) simple to operate, bacterium viability strong adaptability, operational process is without the need to Special controlling.
(2) acidophilic thiobacillus A.ferrivorans directly utilizes the Fe in pickling waste waters
2+for the energy, without the need to adding a large amount of medicaments.
(3) reaction can not generate this Hazardous wastes of pickling mud, can not cause secondary pollution.
(4) jarosite of biological process synthesis comparatively chemical method synthesis there is better homogeneity and more perfect crystal formation, therefore in materials application, have higher potentiality.
(5) the present invention was through the biological respinse time of 8 ~ 10 days, the highlyest synthesized jarosite 3.17g, heavy metal ion (Cr
3+, Ni
2+) clearance best result do not reach 87.02% and 55.30%.
Accompanying drawing explanation
Fig. 1 is the influence curve figure of initial pH to strain activity.
Fig. 2 is the influence curve figure of initial pH to jarosite growing amount.
Fig. 3 is initial Fe
2+concentration is to the influence curve figure of strain activity.
Fig. 4 is initial Fe
2+concentration is to the influence curve figure of jarosite growing amount.
Fig. 5 is the influence curve figure of temperature to strain activity.
Fig. 6 is the influence curve figure of temperature to jarosite growing amount.
Embodiment
A method for biological process synthesis jarosite process pickling waste waters, employing acidophilic thiobacillus A.ferrivorans utilizes the Fe in pickling waste waters
2+for energy organism method synthesis jarosite, remove heavy metal ion wherein, concrete steps are as follows simultaneously:
(1) separation and purification A.ferrivorans: get second pond mud from sewage work (city east, Nanjing sewage work), obtain the A.ferrivorans of pure culture after separation and purification;
(2) pickling waste waters pre-treatment: by pickling waste waters (waste water produced in steel surface oxide process is removed by Steel Plant of Jiangsu Province) with for subsequent use after 0.22 μm of membrane filtration sterilizing;
(3) synthesis of jarosite and the removal of heavy metal: with the pickling waste waters after sterilizing for solution preparation 9K substratum, add the A.ferrivorans bacterium liquid of pure culture, acid adding regulates initial pH, adds FeSO
47H
2o regulates initial Fe
2+concentration, shaking table reacts, and after reaction terminates, generates precipitation as jarosite, removes the heavy metal ion (Cr in pickling waste waters simultaneously
3+, Ni
2+).
First the present invention is the A.ferrivorans by the following method in separation and purification mud.Liquid 9K substratum is selected to carry out enrichment isolation to bacterium liquid.The 9K salts solution after 100ml sterilizing and 4.46gFeSO is added in 250ml Erlenmeyer flask
47H
2o, with the H of 50%
2sO
4regulate about pH2.0, in 30 DEG C, in 180r/m shaking table, isothermal vibration is cultivated, and through three to four Secondary Culture, makes A.ferrivorans become absolute predominance flora.The fresh bacterium liquid being cultured to logarithmic phase is coated 9K solid medium, and in 30 DEG C of incubators, inversion is cultured to and grows single bacterium colony.Choose single bacterial plaque in the ferrous substratum of 20ml liquid, 30 DEG C of shake-flask culture, after bacterium liquid becomes reddish-brown, then it is active to reply to propagate, then is separated once with solid 9K, and microscopy thalli morphology unanimously, namely thinks the bacterial strain obtaining pure culture.
Measure the heavy metal content in pickling waste waters with ICP-AES, the results are shown in Table one.
Table one
| Heavy metal | Cr 3+ | Ni 2+ |
| Content (mg/L) | 3.67 | 4.01 |
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
The impact of initial pH on strain activity and jarosite growing amount is discussed, and the removal effect of heavy metal ion:
The fresh A.ferrivorans bacterium liquid of inoculation 1ml is equipped with in the 250ml Erlenmeyer flask of 150ml 9K substratum to a series of, is placed in 180r/min constant temperature oscillation case and cultivates.The impact of the different initial pH of research, acid adding regulates the initial pH of substratum to be respectively 1.5,2.0,2.5,3.0,3.5, designs initial Fe
2+concentration is 8.9g/L, temperature controls at 30 DEG C.Every day samples, and measures Fe
2+oxidation ratio, reflection bacterium activity; Measure the concentration of total iron ion, the growing amount of reaction jarosite.After reaction terminates, measure heavy metal ion (Cr
3+, Ni
2+) content, calculate removal effect.Can find out that the optimal pH of strain growth is 2.5 by Fig. 1 and Fig. 2.Simultaneously the growing amount of jarosite is by the impact of strain activity, and is unfavorable for the generation of jarosite under the too low condition of pH value.When can find out that initial pH is 2.5 by table two, jarosite growing amount is up to 3.06g, Cr
3+and Ni
2+clearance can reach 82.54% and 51.31%.
Table two
Embodiment 2
Initial Fe is discussed
2+concentration is on the impact of strain activity and jarosite growing amount, and the removal effect of heavy metal ion:
The fresh A.ferrivorans bacterium liquid of inoculation 1ml is equipped with in the 250ml Erlenmeyer flask of 150ml 9K substratum to a series of, be placed in 180r/min constant temperature oscillation case and cultivate.The different initial Fe of research
2+the impact of concentration, adds FeSO
47H
2o regulates the initial Fe of substratum
2+concentration be respectively 0.5g/L, 1.0g/L, 2.0g/L, 5.0g/L, 10g/L, design that initial pH is 2.5, temperature controls at 30 DEG C.Every day samples, and measures Fe
2+oxidation ratio, reflection bacterium activity; Measure the concentration of total iron ion, the growing amount of reaction jarosite.After reaction terminates, measure heavy metal ion (Cr
3+, Ni
2+) content, calculate removal effect.Can be found out as Fe in substratum by Fig. 3 and Fig. 4
2+concentration very low time, bacterium can not obtain enough abilities, active in suppression to a certain extent.The growing amount of jarosite is subject to the impact of strain activity simultaneously, and is unfavorable for the generation of jarosite under the condition that in substratum, iron concentration is too low.Initial Fe can be found out by table two
2+when concentration is 10g/L, jarosite growing amount is up to 3.17g, Cr
3+and Ni
2+clearance can reach 87.02% and 55.30%.
Embodiment 3
The impact of temperature on strain activity and jarosite growing amount is discussed, and the removal effect of heavy metal ion:
The fresh A.ferrivorans bacterium liquid of inoculation 1ml is equipped with in the 250ml Erlenmeyer flask of 150ml 9K substratum to a series of, be placed in 180r/min constant temperature oscillation case and cultivate.The impact of research differing temps, the temperature controlling to cultivate is respectively 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, designs that initial pH is 2.5, initial Fe
2+concentration is 8.9g/L.Every day samples, and measures Fe
2+oxidation ratio, reflection bacterium activity; Measure the concentration of total iron ion, the growing amount of reaction jarosite.After reaction terminates, measure heavy metal ion (Cr
3+, Ni
2+) content, calculate removal effect.Can find out that the optimum temperuture of strain growth is 30 DEG C by Fig. 5 and Fig. 6.Simultaneously the growing amount of jarosite is by the impact of strain activity, and is unfavorable for the generation of jarosite under the too low condition of temperature, illustrates that the formation of jarosite is an endothermic process.When can find out 35 DEG C by table two, jarosite growing amount is up to 2.47g, Cr
3+and Ni
2+clearance can reach 84.54% and 53.18%.
Claims (4)
1. a method for biological process synthesis jarosite process pickling waste waters, is characterized in that, comprise the steps:
(1) separation and purification A.ferrivorans: get second pond mud from sewage work, obtains the A.ferrivorans of pure culture after separation and purification;
(2) pickling waste waters pre-treatment: after being filtered by pickling waste waters, sterilizing is for subsequent use;
(3) synthesis of jarosite and the removal of heavy metal: with the pickling waste waters after sterilizing for solution preparation 9K substratum, add the A.ferrivorans bacterium liquid of pure culture, acid adding regulates initial pH to 1.5 ~ 3.5, adds ferrous ion salt and regulates initial Fe
2+concentration, shaking table reacts, and after reaction terminates, generates precipitation as jarosite, removes the heavy metal ion in pickling waste waters simultaneously.
2. the method for biological process synthesis jarosite process pickling waste waters as claimed in claim 1, it is characterized in that, the separation and purification described in step (1) refers to preparation 9K substratum and adds FeSO
47H
2o, carries out the Secondary Culture of three to four times by mud, adopt double-layer agar technique coating, purifying obtains the A.ferrivorans bacterium liquid of pure culture.
3. the method for biological process synthesis jarosite process pickling waste waters as claimed in claim 1, it is characterized in that, the 0.22 μm of membrane filtration sterilizing of pickling waste waters described in step (2), described pickling waste waters refers to the waste water removed and produce in steel surface oxide process.
4. the method for biological process synthesis jarosite process pickling waste waters as claimed in claim 1, is characterized in that, regulate initial Fe in step (3)
2+concentration controls at 0.5 ~ 10g/L, and ferrous ion salt adopts FeSO
47H
2o, reaction process temperature controls at 15 ~ 35 DEG C, and shaking speed is at 180r/min, and the reaction times is 8 ~ 10 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410766052.XA CN104445827A (en) | 2014-12-12 | 2014-12-12 | Method for synthesizing jarosite to process pickling waste water employing biological method |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862250A (en) * | 2015-05-08 | 2015-08-26 | 周洪波 | Acidophilic iron-oxidizing composite microbial agent and preparation method thereof |
| CN114634257A (en) * | 2022-03-04 | 2022-06-17 | 太原碧蓝水利工程设计股份有限公司 | Method for treating acidic mine water and hydroxyl potassium ferric sulfate synthesized by acidic mine water |
-
2014
- 2014-12-12 CN CN201410766052.XA patent/CN104445827A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 时启立等: "细菌氧化法制取黄钾铁矾的研究", 《环境科学与技术》 * |
| 王长秋等: "钾铁矾类矿物沉淀去除Cr(VI)的初步研究", 《矿物岩石地球化学通报》 * |
| 王长秋等: "黄钾铁矾的形成条件研究及其环境意义", 《岩石矿物杂志》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862250A (en) * | 2015-05-08 | 2015-08-26 | 周洪波 | Acidophilic iron-oxidizing composite microbial agent and preparation method thereof |
| CN114634257A (en) * | 2022-03-04 | 2022-06-17 | 太原碧蓝水利工程设计股份有限公司 | Method for treating acidic mine water and hydroxyl potassium ferric sulfate synthesized by acidic mine water |
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Application publication date: 20150325 |