CN104058565A - Method for treating pickled sludge by using ferrous oxide thiobacillus - Google Patents
Method for treating pickled sludge by using ferrous oxide thiobacillus Download PDFInfo
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- CN104058565A CN104058565A CN201410201370.1A CN201410201370A CN104058565A CN 104058565 A CN104058565 A CN 104058565A CN 201410201370 A CN201410201370 A CN 201410201370A CN 104058565 A CN104058565 A CN 104058565A
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- mud
- heavy metal
- pickling
- thiobacillus ferrooxidant
- sludge
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Abstract
The invention discloses a method for treating pickled sludge by using ferrous oxide thiobacillus, and aims at solving the damage of heavy metal ions (Cr<3+>, Ni<2+>) in the pickled sludge to the environment and the human body. The method aims at the heavy metal ions (Cr<3+>, Ni<2+>) in the pickled sludge, and the heavy metal ions are leached out by using ferrous oxide thiobacillus and are filtered so as to obtain pickled sludge and leachate free of heavy metal ions. The method specifically comprises the following steps: grinding and screening the pickled sludge, dissolving out Ca<2+> by using a NaHCO3 solution, and drying for later use; adding 150ml of 9K culture medium and 1g of pretreated pickled sludge into a conical flask of 250ml, sterilizing at high temperature, adding 1ml of ferrous oxide thiobacillus, controlling the initial temperature to be 30 DEG C, and putting into a shaker in the speed of 180r/min, wherein the initial pH value is 2.3-3, and the concentration of an energy substance Fe<2+> essential for growth and reproduction is 0.5-10g/L. After the reaction time of 8-10 days, the leaching rates of the heavy metal ions Cr<3+> and Ni<2+> are respectively 34.48% to 79.31% and 94.77% to 94.89%.
Description
Technical field
The present invention relates to a kind for the treatment of process of pickling mud, be specifically related to a kind of method of utilizing thiobacillus ferrooxidant to process pickling mud.
Background technology
In the production process of steel industry, inevitably to enter the courses of processing such as annealing, normalizing, quenching, welding, surface can produce the oxide skin of black often.Oxide skin not only affects the visual appearance of steel, also can produce adverse influence to the following process of product, thus need the nitration mixture surfaces such as hydrochloric acid or sulfuric acid, hydrofluoric acid and nitric acid to clean, thus produce the spent pickle liquor that contains the heavy metal ion such as nickel chromium triangle in a large number.At present, steel industry adopts lime neutralization precipitation method to process spent pickle liquor mostly.This method makes water outlet reach emission standard, but causes secondary pollution, produces a large amount of pickling mud.
In pickling mud, contain plurality of heavy metal ion (Cr
3+, Ni
2+), belong to Hazardous wastes (HW17).At present, the main methods of pickling mud has pyrogenic attack technology, curing/stabilizing Landfill and cement kiln disposal technology altogether.Although cost is low, nickel, chromium a large amount of in pickling mud can not be recycled, and have wasted a large amount of useful resources, do not meet the object that china natural resourcesization is disposed.Nickel in recovered acid contaminate mud, chromium etc. not only fundamentally solve heavy metal pollution problem, and make the valuable metals resources such as nickel, chromium obtain regeneration, obtain obvious economic benefit in contaminated solution problem.The treatment process of recovered acid contaminate mud heavy metal ion has at present:
Chinese patent 1 (CN101618892A) discloses a kind of recovery and method of comprehensive utilization of acid-washing stainless steel Heavy Metals in Sludge, and the method adopts the precipitator method from leach liquor, to reclaim chromium, and extraction process reclaims nickel.
Chinese patent 2 (CN102690956A) discloses a kind of green method of extracting chromium and nickel of acid-washing stainless steel mud, and the method adopts H
2sO
4heavy metal ion in acid-washing stainless steel mud is leached, be converted into the Cr in leach liquor
3+, Ni
2+ion.
There is following defect in the treatment process of above-mentioned pickling mud:
(1) described method need to add a large amount of NaOH, H
2o
2, Na
2cO
3deng medicament, nickel chromium triangle is separated from leach liquor with the method for precipitation, easily cause the incomplete of nickel chromium triangle separation.Generate a large amount of precipitations simultaneously, cause secondary pollution, as patent 1.
(2) described method need to consume a large amount of medicaments such as sulfuric acid, and cost is increased greatly, the wasting of resources, and in process, need 80 ℃ of high temperature, operation inconvenience, as patent 2.
Above-mentioned defect causes up to now, applies existing processing method and is difficult to pickling mud to be processed efficiently, and reclaim the valuable heavy metal resources such as nickel chromium triangle wherein.
Summary of the invention
The object of the invention is to for the heavy metal ion (Cr in pickling mud
3+, Ni
2+), with thiobacillus ferrooxidant, heavy metal ion is wherein leached and reclaimed, a kind of method of utilizing thiobacillus ferrooxidant to process pickling mud is provided.
The technical solution that realizes the object of the invention is:
Utilize thiobacillus ferrooxidant to process a method for pickling mud, it is characterized in that: adopt thiobacillus ferrooxidant by the heavy metal ion (Cr in pickling mud
3+, Ni
2+) leach and reclaim, concrete steps are as follows:
(1) separation and purification thiobacillus ferrooxidant: get second pond mud from sewage work, separation and purification obtains the thiobacillus ferrooxidant bacterium liquid of pure culture;
(2) pickling sludge pretreatment: after mud is ground and sieved, use NaHCO
3solution stripping Ca
2+, dry for standby;
(3) leaching of pickling sludge heavy-metal: prepare 9K substratum, add thiobacillus ferrooxidant bacterium liquid and the energy substance Fe of pure culture
2+, acid adding regulates initial pH, and shaking table reaction, after reaction finishes, is leached the heavy metal ion in pickling mud, is converted into the Cr in leach liquor
3+, Ni
2+.
In described step (1), separation and purification refers to preparation 9K substratum and adds FeSO
4h
2o, carries out mud the cultivation of going down to posterity of three to four times, adopts the coating of double-layer plate method, and purifying obtains the thiobacillus ferrooxidant bacterium liquid of pure culture.
NaHCO in described step (2)
3strength of solution is 0.5mol/L.
Initial pH in described step (3) is controlled at 2.3～3.Add the required energy substance Fe of thiobacillus ferrooxidant growth and breeding
2+concentration be 0.5～10g/L.Reaction process is controlled temperature at 30 ℃, and shaking speed is at 180r/min.Reaction times is 8～10 days.
Principle explanation:
Biological treatment is as the state-of-the-art technology of removing Heavy Metals in Sludge, utilize the indirect action of direct effect or its meta-bolites of some microorganisms of occurring in nature, produce oxidation, reduction, complexing, absorption or solvency action, by (as heavy metal, sulphur and other metals) lixiviate of some insoluble composition in solid phase a kind of technology of separating, wherein most widely used is thiobacillus ferrooxidant and thiobacillus thiooxidans.
Compared with prior art, its remarkable advantage is in the present invention:
(1) simple to operate, bacterium viability strong adaptability, operational process is without special control.
(2) can directly with spent acid, regulate medium pH, without consuming a large amount of medicaments such as acid.
(3) biological treatment not only can effectively be removed the heavy metal in mud, can play the effect of killing pathogenic bacteria again simultaneously.
(4) the present invention entered the Bioleaching time of 8～10 days, can make heavy metal Cr
3+, Ni
2+leaching yield reach respectively 34.48%～79.31% and 94.77%～94.89%.
Accompanying drawing explanation
Fig. 1 is Cr
3+influence curve figure to thiobacillus ferrooxidant activity.
Fig. 2 is Ni
2+shadow graphic representation to thiobacillus ferrooxidant activity.
Fig. 3 is Ca
2+shadow graphic representation to thiobacillus ferrooxidant activity.
Fig. 4 is that initial pH is to Ni in pickling mud
2+the influence curve figure leaching.
Fig. 5 is that initial pH is to Cr in pickling mud
3+the influence curve figure leaching.
Fig. 6 is Fe
2+to Ni in pickling mud
2+the influence curve figure leaching.
Fig. 7 is Fe
2+to Cr in pickling mud
3+the influence curve figure leaching.
Fig. 8 is that pretreating sludge and untreated sludge are to Ni
2+the influence curve figure leaching.
Fig. 9 is that pretreating sludge and untreated sludge are to Cr
3+the influence curve figure leaching.
Embodiment
Utilize thiobacillus ferrooxidant to process a method for pickling mud, adopt thiobacillus ferrooxidant by the heavy metal ion (Cr in pickling mud
3+, Ni
2+) leach and reclaim, concrete steps are as follows:
(1) separation and purification thiobacillus ferrooxidant: get second pond mud from sewage work, obtain the thiobacillus ferrooxidant bacterium liquid of pure culture after separation and purification;
(2) pickling sludge pretreatment: after pickling mud is ground and sieved, use NaHCO
3solution stripping Ca
2+, dry for standby;
(3) leaching of pickling sludge heavy-metal: prepare 9K substratum, add thiobacillus ferrooxidant bacterium liquid and the energy substance Fe of pure culture
2+, acid adding regulates initial pH, shaking table reaction, and after reaction finishes, the heavy metal ion in pickling mud leaches, and is converted into the Cr in leach liquor
3+, Ni
2+.
The present invention is the thiobacillus ferrooxidant in separation and purification mud by the following method:
Select liquid 9K substratum to carry out enrichment screening to bacterium liquid.In 250ml Erlenmeyer flask, add 9K salts solution and 4.46gFeSO after 100ml sterilizing
4h
2o, the H with 50%
2sO
4regulate pH2.0 left and right, in 30 ℃, in 180r/m shaking table, isothermal vibration is cultivated, and through three to four cultivations of going down to posterity, makes thiobacillus ferrooxidant become absolute predominance flora.The fresh bacterium liquid that is cultured to logarithmic phase is coated to 9K solid medium, and in 30 ℃ of incubators, inversion is cultured to and grows single bacterium colony.Choose single bacterial plaque to the ferrous substratum of 20ml liquid, 30 ℃ of shake-flask culture, become after reddish-brown until bacterium liquid, then it is active to replying to propagate, then use solid 9K separation once, and microscopy thalli morphology is consistent, think and obtain the bacterial strain of pure culture.
Pickling sludge digestion is measured wherein to heavy metal content in Table 1 by ICP.
| Heavy metal | Cr 3+ | Ni 2+ | Ca 2+ |
| Content (%) | 2.48 | 1.40 | 26 |
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1
Cr in mud is discussed
3+active impact on bacterium:
In 250ml Erlenmeyer flask, add 150ml9K substratum, under 121 ℃ of high temperature, after sterilizing 20min, add the bacterium liquid of 1ml, and the initial pH value of reaction system is adjusted to 2.5, add energy substance Fe
2+concentration 8.9g/L, get 5 duplicate samples, 1 part is blank, uses respectively Cr for all the other 4 parts
2(SO
4)
3regulate Cr in substratum
3+concentration be 150mg/L, 300mg/L, 450mg/L, 600mg/L.In 30 ℃, in 180r/m shaking table, isothermal vibration is cultivated.Sampling every day, measures Fe
2+oxidation ratio, reflection bacterium activity.Cr as seen from Figure 1
3+the activity of bacterium is not had to impact substantially.
Embodiment 2
Ni in mud is discussed
2+active impact on bacterium:
In 250ml Erlenmeyer flask, add 150ml9K substratum, under 121 ℃ of high temperature, after sterilizing 20min, add the bacterium liquid of 1ml, and the initial pH value of reaction system is adjusted to 2.5, add energy substance Fe
2+concentration 8.9g/L, get 5 duplicate samples, 1 part is blank, uses respectively NiSO for all the other 4 parts
4regulate Ni in substratum
2+concentration be 150mg/L, 300mg/L, 450mg/L, 600mg/L.In 30 ℃, in 180r/m shaking table, isothermal vibration is cultivated.Sampling every day, measures Fe
2+oxidation ratio, reflection bacterium activity.Ni as seen from Figure 2
2+the activity of bacterium is had to certain inhibition.
Embodiment 3
Ca in mud is discussed
2+active impact on bacterium:
In 250ml Erlenmeyer flask, add 150ml9K substratum, under 121 ℃ of high temperature, after sterilizing 20min, add the bacterium liquid of 1ml, and the initial pH value of reaction system is adjusted to 2.5, add energy substance Fe
2+concentration 8.9g/L, get 5 duplicate samples, 1 part is blank, uses respectively CaNO for all the other 4 parts
3regulate Ca in substratum
2+concentration be 150mg/L, 300mg/L, 450mg/L, 600mg/L.In 30 ℃, in 180r/m shaking table, isothermal vibration is cultivated.Sampling every day, measures Ca
2+oxidation ratio, reflection bacterium activity.Ca as seen from Figure 3
2+activity inhibition to bacterium is larger.
Because Ca
2+with the SO in substratum
4-produce a large amount of precipitations, the activity of thiobacillus ferrooxidant is had to certain restraining effect.So the present invention carries out pre-treatment to pickling mud: mud is ground to rear mistake 200 mesh sieves, use NaHCO
3solution stripping Ca
2+, dry for standby.
Embodiment 4
Mud is ground to rear mistake 200 mesh sieves, use NaHCO
3solution stripping Ca
2+, dry for standby.In 250ml Erlenmeyer flask, add 150ml9K substratum and 1g pickling mud, under 121 ℃ of high temperature, after sterilizing 20min, add the bacterium liquid of 1mL, and energy substance FeSO
4h
2o, wherein Fe
2+concentration be 8.9g/L.Get four minutes samples, regulate initial pH value to be respectively 2.3,2.5,2.8,3, in 30 ℃, in 180r/m shaking table, isothermal vibration is cultivated.Sampling in every two days, the concentration of mensuration heavy metal nickel chromium triangle.After the leaching cycle of 8～10 days, pickling Heavy Metals in Sludge Cr
3+clearance can reach 79.31%, Ni
2+clearance can reach 94.77%, substantially reach the emission standard of national regulation.By Fig. 4 and Fig. 5, can find out that the reduction of pH is conducive to Cr
3+and Ni
2+leaching.
Embodiment 5
Mud is ground to rear mistake 200 mesh sieves, use NaHCO
3solution stripping Ca
2+, dry for standby.In 250ml Erlenmeyer flask, add 150ml9K substratum and 1g pickling mud, under 121 ℃ of high temperature, after sterilizing 20min, add the bacterium liquid of 1mL, and the initial pH value of reaction system is adjusted to 2.5, get 5 duplicate samples and add respectively energy substance FeSO
4h
2o, wherein Fe
2+concentration be 0.5g/L, 1g/L, 2g/L, 5g/L, 10g/L.In 30 ℃, in 180r/m shaking table, isothermal vibration is cultivated.Sampling in every two days, the concentration of mensuration heavy metal nickel chromium triangle.After the leaching cycle of 8～10 days, pickling Heavy Metals in Sludge Cr
3+clearance can reach 34.88%, Ni
2+clearance up to 94.89%, substantially reach the emission standard of national regulation.By Fig. 3 and Fig. 4, can find out energy substance Fe
2+the increase of dosage is conducive to Cr
3+and Ni
2+leaching.
Comparative example
Pickling mud is ground to rear mistake 200 mesh sieves, use NaHCO
3solution stripping Ca
2+, dry for standby.In 250ml Erlenmeyer flask, add 150ml9K substratum, then add respectively the unpretreated mud of 1g and the pretreated mud of 1g, under 121 ℃ of high temperature, after sterilizing 20min, add the bacterium liquid of 1ml, and the initial pH value of reaction system is adjusted to 2.5, add energy substance Fe
2+concentration be 8.9g/L.In 30 ℃, in 180r/m shaking table, isothermal vibration is cultivated.Sampling in every two days, the concentration of mensuration heavy metal nickel chromium triangle.By Fig. 8 and Fig. 9, can find out that pretreated pickling mud leaching yield improves, Ni
2+leaching yield by 74.48%, bring up to 91.15%, Cr
3+leaching yield by 23.44%, bring up to 47.35%.
Claims (7)
1. utilize thiobacillus ferrooxidant to process a method for pickling mud, it is characterized in that: adopt thiobacillus ferrooxidant by the heavy metal ion (Cr in pickling mud
3+, Ni
2+) leach and reclaim, concrete steps are as follows:
(1) separation and purification thiobacillus ferrooxidant: get second pond mud from sewage work, obtain the thiobacillus ferrooxidant bacterium liquid of pure culture after separation and purification;
(2) pickling sludge pretreatment: after pickling mud is ground and sieved, use NaHCO
3solution stripping Ca
2+, dry for standby;
(3) leaching of pickling sludge heavy-metal: prepare 9K substratum, add thiobacillus ferrooxidant bacterium liquid and the energy substance Fe of pure culture
2+, acid adding regulates initial pH, and shaking table reaction, after reaction finishes, is leached the heavy metal ion in pickling mud, is converted into the Cr in leach liquor
3+, Ni
2+.
2. according to the method described in claims 1, it is characterized in that: in described step (1), separation and purification refers to preparation 9K substratum and adds FeSO
4h
2o, carries out mud the cultivation of going down to posterity of three to four times, adopts the coating of double-layer plate method, and purifying obtains the thiobacillus ferrooxidant bacterium liquid of pure culture.
3. according to the method described in claims 1, it is characterized in that: the NaHCO in described step (2)
3strength of solution is 0.5mol/L.
4. according to the method described in claims 1, it is characterized in that: the initial pH in described step (3) is controlled at 2.3～3.
5. according to the method described in claims 1, it is characterized in that: in described step (3), add the required energy substance Fe of thiobacillus ferrooxidant growth and breeding
2+concentration be 0.5～10g/L.
6. according to the method described in claims 1, it is characterized in that: the temperature of the reaction in described step (3) is controlled at 30 ℃, and shaking speed is at 180r/min.
7. according to the method described in claims 1, it is characterized in that: the reaction times in described step (3) is 8～10 days.
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|---|---|---|---|
| CN201410201370.1A CN104058565A (en) | 2014-06-28 | 2014-06-28 | Method for treating pickled sludge by using ferrous oxide thiobacillus |
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|---|---|---|---|
| CN201410201370.1A CN104058565A (en) | 2014-06-28 | 2014-06-28 | Method for treating pickled sludge by using ferrous oxide thiobacillus |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373544A (en) * | 2019-07-25 | 2019-10-25 | 中国科学院过程工程研究所 | A kind of Deep-Sea Microorganisms gradient handles the device and method of metal ion in heavy metal sewage sludge |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375553A (en) * | 2002-04-25 | 2002-10-23 | 南京农业大学 | Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith |
| CN101830616A (en) * | 2010-05-11 | 2010-09-15 | 沈阳建筑大学 | Method for removing heavy metal Cr from sludge by bioleaching |
| CN103086580A (en) * | 2012-11-21 | 2013-05-08 | 福建省亚热带植物研究所 | Method for quickly removing heavy metals in municipal sludge |
-
2014
- 2014-06-28 CN CN201410201370.1A patent/CN104058565A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375553A (en) * | 2002-04-25 | 2002-10-23 | 南京农业大学 | Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith |
| CN101830616A (en) * | 2010-05-11 | 2010-09-15 | 沈阳建筑大学 | Method for removing heavy metal Cr from sludge by bioleaching |
| CN103086580A (en) * | 2012-11-21 | 2013-05-08 | 福建省亚热带植物研究所 | Method for quickly removing heavy metals in municipal sludge |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373544A (en) * | 2019-07-25 | 2019-10-25 | 中国科学院过程工程研究所 | A kind of Deep-Sea Microorganisms gradient handles the device and method of metal ion in heavy metal sewage sludge |
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Application publication date: 20140924 |