CN1590530A - Acid resistant saccharomycete and its method of biological removing heavy metal in sudge - Google Patents
Acid resistant saccharomycete and its method of biological removing heavy metal in sudge Download PDFInfo
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- CN1590530A CN1590530A CN 200410044843 CN200410044843A CN1590530A CN 1590530 A CN1590530 A CN 1590530A CN 200410044843 CN200410044843 CN 200410044843 CN 200410044843 A CN200410044843 A CN 200410044843A CN 1590530 A CN1590530 A CN 1590530A
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Abstract
An acid-resistant rhodotorula R30 (CGMCC No.1147) for removing heavy metals from sludge is disclosed. The process for removing heavy metals from sludge includes loading the sludge in bioreactor, inoculating said rhodotorula R30 and thiobacillus TS6, aerating at 28 deg.C for 2-6 days, dewatering of sludge, regulating pH of liquid phase for depositing heavy metals, and neutralizing solid phase for agricultural purpose.
Description
One, technical field
The present invention relates to a kind of acid resistance rhodotorula bacterium and be used for the method that sludge organism removes heavy metal, is a technology of utilizing yeast and thiobacillus to remove heavy metal in municipal sludge and the industrial sludge mutually, belongs to field of environment engineering technology.
Two, technical background
The annual generation of China all kinds of industrial sludge and the city municipal sludges that contain heavy metal a large amount of, that demand safe disposal urgently.Though it is cheap that the utilization of mud soil is considered to disposal costs for many years always, and can realize the approach that recycling sludge utilizes, but (Cu, Zn, heavy metal content such as Cr, Ni can reach hundreds ofly to thousands of mg/kg in the most municipal sludges of China, and Cr content can reach 1%～4% in industrial sludge such as the leather-making mud because the existing of toxic heavy metal in the mud; Heavy metal can reach 10% even higher in the electroplating sludge), the potentially contaminated of heavy metal is the problem that people worry all the time in the utilization of mud soil, resistance that mud is agricultural and dispute are also very big always.And adopt other treatment processs, for example sludge incineration, mud to do building materials, heap such as fills out at the anxiety that still has heavy metal harm.From mud, remove heavy metal, mud " cleaning " is changed, be convenient to the mud regeneration, crucial meaning is arranged.
Heavy metal is mainly with the sulfide of insoluble in the mud, the organism combined, and forms such as precipitation attitude are present in the solid phase of mud.Remove the heavy metal in the mud, must manage heavy metal is dissolved out from solid phase.Past has the investigator to adopt chemical extraction method, utilize processing mud such as mineral acid or complexing agent with dissolving and lixiviate heavy metal to reach the purpose of heavy metal in the removal mud.But the chemical process acid consumption is big, processing costs is high, operation is dangerous, is difficult to be committed to engineering reality, and to the removal effect of some heavy metal relatively poor (clearance as Cu is lower than 50%, and the clearance of Cr is lower than 40%).
In recent years, there is the investigator to attempt to utilize microbial process to dissolve and removes heavy metal in the mud.United States Patent (USP) 5,217,615 and 5,454,948 disclose a kind of method that adopts the removal of microorganisms sludge heavy-metal, and it is to utilize thiobacillus thiooxidans and grate sulfur thiobacillus to produce sulfuric acid with elementary sulfur as energy substance to dissolve heavy metal in the removal mud.But the main poisonous heavy metal Cr in the mud can not effectively be removed, and its clearance only is 13～57%.
Two patents that this seminar applies in earlier stage, the method of thiobacillus ferrooxidant and removal sludge heavy-metal thereof, number of patent application is 02112924.X, biological eliminating method number of patent application 02137921.1 with chromium in thiobacillus thiooxidans and the leather-making mud, the former provides a kind of thiobacillus ferrooxidant and has removed the method for sludge heavy-metal, utilizes isolating thiobacillus ferrooxidant Thiobacillus ferrooxidans LX in the mud
5, oxidation substrates is produced acid dissolving heavy metal, and solid-liquid separation is removed heavy metal then.The latter is isolating thiobacillus thiooxidans ThiobacillusthiooxidansTS from leather-making mud
6Remove the chromium in the leather-making mud, make the clearance of Cr reach more than 90%, plant nutrient N, P and organic retention rate are more than 80% in the mud.
But, thiobacillus ferrooxidant and thiobacillus thiooxidans all are the obligate chemoautotrophic bacterias, the particularly low-molecular-weight organic acid of water soluble organic substance is had certain susceptibility, and water soluble organic substance (in water-soluble organic carbon DOC) content can reach 500～1500mg/L in the mud.Therefore, in the system that takes as the leading factor with single thiobacillus, often be difficult to guarantee the stable of biological removal effect, inoculation is the heterotrophic bacterium in energy derive and material source with the water soluble organic substance, be mainly yeast, can reduce the concentration of these deleterious small molecules in mud significantly, help the stripping of thiobacillus Thiobacillus to heavy metal in the mud, remove efficient and the treatment time of shortening more than 2 days thereby improve sludge heavy-metal, for the actual engineering of this technological direction provides technical guarantee.
Three, summary of the invention
Technical problem
The object of the present invention is to provide a kind of heterotrophic microorganism rhodotorula bacterium and be used for the method that sludge organism removes heavy metal, yeast is an eukaryotic microorganisms, utilize the water soluble organic substance growth and breeding in the mud, consume the water soluble organic substance in the mud, eliminated the murder by poisoning of water soluble organic substance, improved the growth activity of thiobacillus, shortened the cycle that sludge heavy-metal is removed autotrophic bacteria Thiobacillus sp., reduce power consumption, reduce cost.
Technical scheme
Yeast provided by the invention separates from process hides mud, name rhodotorula Pseudomonas (Rhodotorula sp.) R30, and this strain characteristics is: unicellular, be oval, diameter 4.5～5.5 μ m, budding.Do not produce thecaspore.Bacterium colony is the cement sample, produces pink pigment, forms pod membrane.Nonfermented sugar can not utilize inositol to make sole carbon source, does not form the kind of starch compound, can assimilate KNO
3(NH
4)
2SO
4Yeast R30 nutritional requirement is simple, is easy to enlarged culturing, is inoculated in the PDA substratum, and 28 ℃～30 ℃, pH=3～7 o'clock, well-grown.When pH＜3.0, growth is subjected to certain influence, but still can tolerate the sour environment about pH2.And can utilize the water soluble organic substance growth in the mud, inoculation yeast R30 lawn one encircles in the sludge water soluble organism, cultivates 96h on 28 ℃ shaking table, and the amount of DOC is reduced to 345mg/L from 1485mg/L in the mud, reduced 77%, and saccharomycetic quantity reaches 4.8 * 10
7Individual/mL.
Yeast R30 and be applied to the method that sludge organism removes heavy metal is characterized in that:
1, the separation of yeast R30 and enlarged culturing, preparation PDA substratum, composition: potato 200g, sucrose or glucose 20g, water 1000mL, pH nature, 121 ℃, 30min sterilization.Its separation method: draw the 1mL leather-making mud in the 9ml sterilized water, make serial dilution, the diluent 0.1mL that gets suitable gradient coats on the PDA flat board, cultivate 48h in 28 ℃, picking pink bacterium colony, film-making, dyeing, microscopy, observing diameter is the oval thalline of 0.5 μ m, and the purifying of further ruling on the PDA flat board, obtains single bacterium colony of form unanimity, the switching inclined-plane, it is standby to be stored in 4 ℃ of refrigerators.The liquid culture condition: get yeast R30 lawn from the inclined-plane, be inoculated in the PDA liquid nutrient medium, 28～30 ℃, to cultivate 2 days in the reciprocating type shaking table of 180rpm, the bacterium number reaches 10
8Individual/mL.
2, yeast R30 can make in the medium that solvability is organic to be reduced more than 70%, and can tolerate the sour environment about pH2.
3, thiobacillus Thiobacillus sp. is mainly this laboratory strain separated Thiobacillus thiooxidans TS
6(CGMCC NO.0759).Its culture condition and number of patent application are that the biological eliminating method of chromium in 02137921.1 thiobacillus thiooxidans and the leather-making mud is identical.
4, in bio-reactor, add pending mud and 0.5～30g/L elemental sulfur, and inoculate 3%～7% thiobacillus and 1%～3% yeast R30 respectively, under 28 ℃, ventilate and stir process 2-6 days (when purpose heavy metal solubility rate reaches 95% when above, end treatment), pump the mud of handling.
5, the mud of above-mentioned processing is through sedimentation, and the sedimentation mud with 10～20% is back to and replaces acclimation sludge usefulness in the bio-reactor, adds pending mud and 0.5～30g/L elemental sulfur, circular treatment.
6, residual settlement mud carries out processed, the liquid phase part that obtains removing the solid phase part of heavy metal and contain heavy metal.
7, the liquid phase part that contains heavy metal is regulated pH by dropping into alkaline matter (magnesium oxide, lime and sodium hydroxide), make heavy metal precipitation wherein after, supernatant liquor enters sewage work and handles.
8, mud process sedimentation, processed, the liquid phase part that obtains removing the solid phase part of heavy metal and contain heavy metal.
9, the liquid phase part that contains heavy metal is regulated pH by dropping into alkaline matter, make heavy metal precipitation wherein after, draining enters Sewage Plant and handles.
10, the solid phase part that removes behind the heavy metal is directly agricultural after with alkaline matter (lime and ammoniacal liquor etc.) neutralization, or further directly is prepared into organic commercial fertilizer or matrix.
Know-why of the present invention is: add yeast in reaction, yeast utilizes the water soluble organic substance growth and breeding in the mud, consume the water soluble organic substance in the mud, reach elimination or lower the effect that water soluble organic substance is poisoned autotrophic bacteria Thiobacillus sp., to improve the growth activity of thiobacillus, shorten the cycle that sludge heavy-metal is removed, reduce cost.
Beneficial effect:
Yeast provided by the invention and be used for the method that sludge organism removes heavy metal has following beneficial effect:
1, yeast R30 provided by the invention, separation is from process hides mud, unicellular eukaryotic microorganisms, nutritional requirement is low, and growth conditions is extensive, be easy to enlarged culturing, water soluble organic substance in the mud satisfies the growth requirement of yeast R30 substantially, and inoculation yeast bacterium R30 cultivates 96h at 28 ℃ in the sludge water soluble organism, the amount of DOC is reduced to 345mg/L from 1485mg/L in the mud, has reduced 77%.
2, utilize yeast R30 provided by the invention and thiobacillus composite methods, the pH lowering speed is fast in the reaction solution, and the treatment time significantly shortens, heavy metal solubility rate height, and especially the solubility rate of Cr reaches 95%～100%.
3, yeast R30 extensively is present in the environment, experimental results show that to be non-pathogenic bacteria, and is harmless to human body and animal.
4, compare with chemical extraction method, reaction temperature of the present invention and, operating environment close friend does not produce secondary pollution, running cost is cheap.Chemical extraction method is removed in the operating process of sludge heavy-metal, owing to need add a large amount of mineral acids, the sludge reaction abundant with organic matter produces a large amount of bubbles and stink, makes severe operational environment.And the present invention utilizes multiple microorganism compound action, and wherein heterotrophic bacterium consumes organism, reduces the murder by poisoning of organism to autotrophic bacteria, promote the autotrophic bacteria growth activity and produce acid, and the biological respinse gentleness, non-secondary pollution produces.
5, after this method is handled plant nutrient N, P in the mud and organic retention rate more than 80%, the retention rate 80-85% of N wherein, P is 75-80%, organic matter is 85-85%;
Four, embodiment
Embodiment 1:
(1) sampling
Get the concentration basin mud of Zhejiang leather-making waste water treatment plant, this leather-making mud essential property sees Table 1.
Table 1 is for the essential property of trial-production leather mud
PH Cr solid content N P organic matter
mg/kg????-------------???％???-------------
8.21???14730????4.84??????2.83???????0.81????45.68
(2) cultivation of yeast R30
Preparation PDA substratum, potato 200g, sucrose or glucose 20g, water 1000mL, pH nature, 121 ℃, 30min sterilization.The liquid culture condition: get yeast R30 lawn from the PDA medium slant, be inoculated in the PDA liquid nutrient medium, 28～30 ℃, to cultivate 2 days in the reciprocating type shaking table of 180rpm, the bacterium number reaches 10
8Individual/mL.
(3) thiobacillus bacterial strain
Thiobacillus Thiobacillus thiooxidans TS
6, be that bacterial strain is preserved in this laboratory, to preserve at China Committee for Culture Collection of Microorganisms common micro-organisms center, registration number is CGMCC NO.0759.This bacterium is the inorganic chemoautotrophic bacteria of obligate.
(4) Cr biological eliminating reaction in the leather-making mud
Add 1.0g/L sulphur powder in the leather-making mud, the Thiobacillus thiooxidans TS of inoculation 10%
6, 3% Rhodotorula sp.R30, the 180rpm shaking culture was handled 5～6 days in shaking table, and the control treatment that does not add R30 is set, every day the assaying reaction pH variation of media.After reaction finishes, measure Cr solubility rate in the mud.In the measuring reaction solution during pH=2.0, the solubility rate 70% of Cr, in the reaction solution during pH=1.7, the solubility rate 85% of Cr, in the reaction solution during pH=1.5, the solubility rate 100% of Cr.Table 2 shows the variation of pH in the different treatment reaction solution and the stripping situation of chromium, adds the yeast processing and compares the about 28h of reaction times shortening with contrast.
The solubility rate % of the changing conditions of pH and chromium in the table 2 different treatment reaction solution
| Time (h) | 0????24????48????72????96????120????148 | |
| ?TS 6+R30 | ?pH | 5.6??4.3???2.9???2.1???1.7???1.5 |
| Cr solubility rate % | 0????10????46????69????85????99.8 | |
| ?TS 6 | ?pH | 5.6??4.2???3.5???2.8???2.0???1.8????1.6 |
| Cr solubility rate % | 0????12????32????45????74????85?????100 |
(5) handle the solid-liquid separation of back mud and the recycling of chrome waste liquid
See patent " biological eliminating method of chromium in thiobacillus thiooxidans and the leather-making mud " (number of patent application 02137921.1) in this seminar early stage, that is: above-mentioned processing mud obtains chrome waste liquid and takes off the chromium sludge filter cake after centrifugal.Take off the chromium sludge filter cake and meet pollutent control criterion (GB4284-84) in the agricultural mud fully, in unslaked lime and after can as fertilizer sources use.Chrome waste liquid adds MgO and makes Cr in the chrome waste liquid
3+Become Cr (OH)
3The precipitation, again with behind the sulfuric acid dissolution as chrome tanning agent.
Embodiment 2:
(1) sampling: get the concentration basin mud of municipal sewage plant, Jiangsu, this mud fundamental characteristics sees Table 3.
Table 3 is for examination mud fundamental characteristics
PH contains the organic Zn Cr of solid N P Cu
Rate
-------------??％??-------------????-------------mg/kg-------------
7.56????3.34????2.69????1.15????????43.7?????1578????????310??????????522
(2) cultivation of yeast R30 is with embodiment 1
(3) Thiobacillus thiooxidans TS
6Bacterial strain: with embodiment 1
(4) Zn, Cr, the reaction of Cu biological eliminating in the municipal sludge
Add the 5g/L elemental sulfur in the municipal sludge, the Thiobacillus thiooxidans TS of inoculation 10%
6, 3% Rhodotorula sp.R30, the 180rpm shaking culture was handled 4～6 days in shaking table; The control treatment do not add Rhodotorula sp.R30 is set, every day the assaying reaction pH variation of media.After reaction finishes, measure the solubility rate of Cr, Zn, Cu in the mud.The stripping situation of the variation of pH and Cr, Zn, Cu sees Table 4 in the different treatment reaction medium, adds the yeast processing and shortens 56h at least with the complete dissolution time that chromium is compared in contrast, and the complete dissolution time of zinc shortens 48h, and the complete dissolution time of copper shortens 50h at least.
The solubility rate % of the changing conditions of pH and chromium, zinc, copper in the table 4 different treatment reaction solution
| Time (h) | 0????24????48????72???96?????120???144 | |
| ?TS 6+R30 | ?pH | 6.2??4.0???2.1???1.7??1.5????1.5???1.4 |
| Cr solubility rate % | 0????15????70????85????95????100???--- | |
| Zn solubility rate % | 0????65????100???---???---???---???--- | |
| Cu solubility rate % | 0????18????38????89????100???---???--- | |
| ?TS 6 | ?pH | 6.2??4.1???2.8???2.5???2.4???2.2???2.0 |
| Cr solubility rate % | 0????15????30????50????52????55????68 | |
| Zn solubility rate % | 0????30????64????90????100???---???--- | |
| Cu solubility rate % | 0????16????29????38????40????60????82 |
Five, description of drawings
Fig. 1 utilizes the rhodotorula bacterium to be used for the method flow diagram that the mud heavy metal biological removes.
Claims (9)
1, rhodotorula Pseudomonas (Rhodotorula sp.) R30, preserve at China Committee for Culture Collection of Microorganisms common micro-organisms center, and preservation date is on May 13rd, 2004, and preservation registration number is CGMCC No.1147; This strain characteristics is: unicellular, be oval, diameter 4.5～5.5 μ m, budding.Do not produce thecaspore.Bacterium colony is the cement sample, produces pink pigment, forms pod membrane.Nonfermented sugar can not utilize inositol to make sole carbon source, does not form the kind of starch compound, can assimilate KNO
3(NH
4)
2SO
4Nutritional requirement is simple, is easy to enlarged culturing, is inoculated in the PDA substratum, and 28 ℃～30 ℃, pH=3～7 o'clock, well-grown.
2, according to claim 1, rhodotorula Pseudomonas (Rhodotorula sp.) R30 is characterised in that the acidic medium environment that can tolerate about pH2.
3, according to claim 1, rhodotorula Pseudomonas (Rhodotorula sp.) R30 is characterised in that and can makes in the medium solvability organic content reduce more than 70%.
4, according to claim 1, rhodotorula bacterium R30 and thiobacillus Thiobacillus sp. remove the method for heavy metal in municipal sludge and the industrial sludge mutually, it is characterized in that:
1) in mud, adds 1%～3% R30 bacterial strain and 3%～7% thiobacillus Thiobacillus sp., under 28 ℃ and aeration-agitation condition, act on 2-6 days, pump the mud of handling;
2) mud of above-mentioned processing is through sedimentation, and the sedimentation mud with 10～20% replaces acclimation sludge usefulness to bio-reactor, add pending mud and 0.5～30g/L elemental sulfur, circular treatment;
3) residual settlement mud carries out processed, the liquid phase part that obtains removing the solid phase part of heavy metal and contain heavy metal;
4) liquid phase part that contains heavy metal is regulated pH by dropping into alkaline matter, make heavy metal precipitation wherein after, draining enters Sewage Plant and handles.
5, yeast according to claim 4 and be used for the method that sludge organism removes heavy metal is characterized in that: the compound mutual work of rhodotorula bacterium R30 and thiobacillus Thiobacillus sp..
6, yeast according to claim 4 and be used for the method that sludge organism removes heavy metal, it is characterized in that: wherein remove behind the heavy metal the solid phase part through with in the alkaline matter and after directly agricultural, or be prepared into organic commercial fertilizer or matrix after further handling by fermentation.
7, yeast according to claim 4 and be used for the method that sludge organism removes heavy metal, it is characterized in that: used alkaline matter refers to magnesium oxide in its method, lime, sodium hydroxide, ammoniacal liquor.
8, yeast according to claim 6 and be used for the method that sludge organism removes heavy metal, it is characterized in that: used alkaline matter refers to lime and ammoniacal liquor in its method.
9,, it is characterized in that according to claim 4 or 6 described yeast and be used for the method that sludge organism removes heavy metal:
Used alkaline matter refers to unslaked lime in its method.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293201C (en) * | 2005-09-19 | 2007-01-03 | 南京农业大学 | Improvement of plate detection ratio of self-culture sulbacillus with chemical energy |
| CN101428929B (en) * | 2008-12-09 | 2010-08-25 | 中南大学 | Method for direct advanced treatment for heavy metal wastewater with biological agent |
| CN102875210A (en) * | 2012-11-06 | 2013-01-16 | 南京农业大学 | Method for co-composting of blue-green algae and polluted bottom sediment |
| CN105439406A (en) * | 2014-07-01 | 2016-03-30 | 北京中科国通环保工程技术有限公司 | Purified terephthalic acid sludge bioleaching method |
| CN107056000A (en) * | 2017-06-13 | 2017-08-18 | 江苏凯米膜科技股份有限公司 | A kind of biochemistry combination conditioning device and its method |
| CN109250878A (en) * | 2018-09-29 | 2019-01-22 | 广东省生态环境技术研究所 | A method of Heavy Metals in Sludge is removed using free nitrous acid |
| CN112321132A (en) * | 2020-12-04 | 2021-02-05 | 河南工程学院 | Municipal sludge treatment and utilization method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5217615A (en) * | 1991-02-25 | 1993-06-08 | Institut National De La Recherche Scientifique | Bacterial leaching process and composition |
| CN1155696C (en) * | 2002-04-25 | 2004-06-30 | 南京农业大学 | Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith |
| CN1169945C (en) * | 2002-07-09 | 2004-10-06 | 周立祥 | Thiobacillus thiooxidans and biological eliminating method of chromium in tanning sludge |
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2004
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293201C (en) * | 2005-09-19 | 2007-01-03 | 南京农业大学 | Improvement of plate detection ratio of self-culture sulbacillus with chemical energy |
| CN101428929B (en) * | 2008-12-09 | 2010-08-25 | 中南大学 | Method for direct advanced treatment for heavy metal wastewater with biological agent |
| CN102875210A (en) * | 2012-11-06 | 2013-01-16 | 南京农业大学 | Method for co-composting of blue-green algae and polluted bottom sediment |
| CN105439406A (en) * | 2014-07-01 | 2016-03-30 | 北京中科国通环保工程技术有限公司 | Purified terephthalic acid sludge bioleaching method |
| CN107056000A (en) * | 2017-06-13 | 2017-08-18 | 江苏凯米膜科技股份有限公司 | A kind of biochemistry combination conditioning device and its method |
| CN107056000B (en) * | 2017-06-13 | 2020-06-30 | 江苏凯米膜科技股份有限公司 | Biological-chemical combined conditioning equipment and method thereof |
| CN109250878A (en) * | 2018-09-29 | 2019-01-22 | 广东省生态环境技术研究所 | A method of Heavy Metals in Sludge is removed using free nitrous acid |
| CN112321132A (en) * | 2020-12-04 | 2021-02-05 | 河南工程学院 | Municipal sludge treatment and utilization method |
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| CN1314797C (en) | 2007-05-09 |
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Assignee: GENERAL TREATMENT ENVIRONMENT (BEIJING) LTD. Assignor: Nanjing Agricultural University Contract record no.: 2011110000042 Denomination of invention: Acid resistant saccharomycete and its method of biological removing heavy metal in sudge Granted publication date: 20070509 License type: Exclusive License Open date: 20050309 Record date: 20110616 |
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Application publication date: 20050309 Assignee: Beijing Zhongke national environmental protection engineering technology Limited by Share Ltd Assignor: Nanjing Agricultural University Contract record no.: 2015990000952 Denomination of invention: Acid resistant saccharomycete and its method of biological removing heavy metal in sudge Granted publication date: 20070509 License type: Exclusive License Record date: 20151116 |
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