CN106115931B - The method that sponge iron cooperates with removing sulfate and Cd (II) waste water with microorganism - Google Patents
The method that sponge iron cooperates with removing sulfate and Cd (II) waste water with microorganism Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/346—Iron bacteria
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The method that the invention discloses sponge iron to cooperate with removing sulfate and Cd (II) waste water with microorganism；This method is under anaerobic, the bacteria suspension C of sponge iron solution A, the bacteria suspension B of sulfate reducing bacteria and iron-reduced tuftedmonas is mixed with volume ratio for 1:1:1~1:3:4, it is aged 40-60min, after reaction, it is washed with deionized deoxygenated water, is impregnated in sterile saline repeatedly；Obtain sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixture；Gained sponge iron is mixed with sulfate reducing bacteria/iron-reducing bacterium mixture with sulfate and Cd (II) waste water, is reacted 20 hours or more under room temperature, while purifying waste water sulfate and Cd (II).The present invention reaches 85% or more to the removal rate of Cd (II) metal, and required equipment is simple and convenient to operate, and reaction is completed at normal temperatures and pressures, and product is solid phase, and reaction system is liquid phase, and product can be easily separated, and is suitable for scale industrial production.
Description
Technical field
The present invention relates to the methods of advanced treatment of wastewater, specifically processing containing sulfate and heavy metal Cd (II) concentration
The deep treatment method of exceeded sewage.
Background technique
Cadmium wastewater is acknowledged as one of environmentally hazardous public hazards of current most serious.The pollution of Cadmium In The Water Body mainly from
Rainwash and industrial wastewater.It is higher containing cadmium in the waste water that sulphur iron ore extracting sulfuric acid and while producing phosphate fertilizer by rock phosphate in powder are discharged,
Every liter of waste water containing cadmium up to tens of to hundreds of micrograms, Pb-Zn deposits and non-ferrous metal metallurgy, burning, plastic products in atmosphere
The cadmium particle formed is burned all possibly into water；Make the catalyst, pigment, stabilizer for plastics, synthetic rubber vulcanization of raw material with pot
The cadmium of the discharges such as agent, fungicide can also pollute water body, during urban water, often due to the dirt of container and pipeline
Dye can also be such that cadmium content in drinking water increases.The discharge of industrial wastewater is higher than coastal seawater and the intracorporal cadmium content of planktonic organism
The cadmium content of off-lying sea, industrial area surface water is higher than non-industrial area.At environmental pollution, such as waste Ni-Cd battery.
Then cadmium leads to cereal, vegetables, livestock and poultry to the pollution that the pollution of environment is to soil and water body first
Cadmium pollution finally enters human body, leads to human poisoning.The maximum murder by poisoning of cadmium is that it can be accumulated by food chain, is rich long-pending, with
Cause directly acts on human body and causes serious disease or promote the generation of chronic disease.After cadmium poisoning, it is mainly shown as kidney function
Obstacle, osteoporosis and softening make one to feel that gnawing pains take no rest all day, nuisance disease --- the Itai-itai diseases of nineteen sixty-eight Japan discovery, just
It is the prominent example of cadmium poisoning, the case where contaminated area cadmium poisoning also occurs in China.
Cadmium content in " water environment quality standard " (GB3838-2002) promulgated in 2002 in I class water of regulation must
0.001mgL must be lower than-1, the cadmium content in II~IV class water has to be lower than 0.005mgL-1, the cadmium content in V class water is not
More than 0.01mgL-1." agricultural irrigation water quality standard " (GB 5084-92) regulation cadmium content has to be lower than 0.005mgL-1。
" integrated wastewater discharge standard " (GB 8978-1996) provides that the highest of the total cadmium of pollutant allows concentration of emission to be 0.1mgL-1。
" sewage is discharged into city sewer water standard " (CJ 3082-1999) regulation sewage is discharged into cadmium in city sewer pollutant
Highest allows concentration of emission to be 0.1mgL-1。
Cadmium causes the attention of countries in the world to the murder by poisoning of human body, and China national environmental law regulation, cadmium is a class of pollutant,
Not handy dilution method replaces necessary processing.And the concentration of the cadmium wastewater of general factory cadmium before treatment is all much higher than state's domestic discipline and family rules
(the highest permissible discharge concentration of cadmium in industrial wastewater is 0.1mgL to fixed standard-1), so cadmium wastewater is necessary before discharging
It is handled, carries out qualified discharge, containing also must properly being stacked every waste, in case rain drop erosion, causes soil, water pollution.
Currently, main removal technology has physical-chemical process, absorption method and bioanalysis etc. for cadmium wastewater.Wherein, it sinks
Shallow lake method advantage is that neutralizer is cheap, and simple process, sediment water content is low, the disadvantage is that sediment weight is big, the water hardness is high out, reaction
Speed is slower, and the sediment stacked will cause secondary pollution.Iron oxidizing process technical process is simple, and treatment conditions are mild, but administers
The problem of it is relatively narrow that effect is obviously used in combination face, is generally used for handling specific sewage, and brings there are many more technical combinations.Drift
The good scope of application of white powder oxidative treatment effect is narrow, the disadvantage is that being only applicable to the electroplating wastewater containing cyanogen, cadmium, and waste residue containing cadmium
Processing be also the problem of requiring study.Electrolysis method cadmium removal rate is high, and recoverable is widely used in the improvement of waste water, but
Cost is relatively high, it is general it is concentrated after be electrolysed better economic benefit again, limit the application of electrolysis method.Absorption method removal effect
Fruit is good, however control condition is relatively more, and practical operation is difficult.Ion-exchange purification degree is high, cadmium can be recycled, without secondary dirt
Dye, but the problem of there is also higher costs.Membrane separation process removal rate is high, can recycle the cadmium salt in waste water, simple process, but film
Selectivity it is relatively high, different waste water must study matched film, the ingredient of waste water also must it is more stable,
Membrane module designs are difficult, invest also relatively high.Bioremediation technology is at low cost, high-efficient, easy to operate, without secondary pollution, so
And there is the microorganism of special degradation capability type in the environment, negligible amounts, while being in a disadvantageous position in interspecies competition.It is raw
Object reinforcement technique has the advantages that bioremediation technology, good development prospect, but fixation support are at high cost, service life is short.
As a kind of novel zeroth order iron material, sponge iron shows stronger place during handling water pollutant
Reason ability.Relative to other zeroth order iron materials, iron filings and iron powder need secondary rust removal, and specific surface area is small, and there are secondary dirts
The defect low with removal efficiency is contaminated, nanometer iron powder preparation cost is higher, is easy to secondary oxidation, has potential environment and biology poison
Property.Sponge iron has large specific surface area, specific surface energy height, stronger electrochemistry enrichment, strong reducing property, physical absorption and flocculation heavy
The superior physical and chemical performances such as shallow lake.Since sponge iron main component is iron, loose porous internal structure, the ratio table provided
Area is 5-10 times of common iron filings, can make oxygen and iron in water that thorough oxidation reaction rapidly occur, lead to filtering type and remove shallow lake side
Formula is excluded, to pipeline, boiler recirculated water dissolved oxygen corrosion, after processing water dissolved oxygen content can reach 0.005mg/L with
Under, it can effectively reinforced anaerobic process.Sponge iron all has very well the pollutants such as organic matter, heavy metal and inorganic salts in water body
Removal capacity, be the zeroth order iron material of a kind of great potential.It is reported that sponge iron and microorganism form a kind of immobilization biological
System, at optimum conditions, water outlet TP can be down to 0.5mg/L or less, and (Zhang Lidong, sponge iron cooperate with mutually rush dephosphorization to grind with microorganism
Study carefully [J]).When pH value is 5, reaction 1h, sponge iron can reach 0.30mg/g (Gu Yingying, spongy iron reducing water to nitrate reduction
The Primary Study [J] of middle nitrate).And for heavy metal, under certain initial concentration, optimal pH, temperature and partial size, sponge
Iron can reach 0.18mg/g to the removal of Cr (VI) (Sun Yingxue, sponge iron handle Cr dynamics [J]).
Sulfate reducing bacteria (SRB) handles heavy metal wastewater thereby, is the S generated under anaerobic using SRB2-In waste water
Heavy metal ion reaction, generate metal sulfide precipitating with heavy-metal ion removal, SRB pure culture processing method has separation
Purification is many and diverse, operating condition is harsh, strain is lost the problems such as big.And anaerobic sludge method can provide sludge load for SRB strain
Body forms a metastable environment.But common anaerobic sludge flocculation structure is loose, and settling property is poor, unit microorganism
The problem of content is few, and activity is not high, and there is also strain losses.Therefore, it is necessary to which SRB strain sludge immobilization to be handled to a huge sum of money
Belong to waste water.
Summary of the invention
It is an object of that present invention to provide the effect of a kind of performance sponge iron, sulfate reducing bacteria and iron-reducing bacterium coordinated,
85% or more is reached to the removal rate of Cd (II) metal, is significantly higher than removal when sponge iron and sulfate reducing bacteria independent role
Efficiency, and make the sponge iron of the synchronous removal of heavy metal in waste water Cd (II) and sulfate cooperateed with microorganism removing sulfate and
The method of Cd (II) waste water.
Iron also pathogenic microorganism is often referred to the microorganism with dissimilatory reduction Fe (III) function.Alienation Fe (III) reduction is anaerobism
It is that electronics supplies that important one of Biochemical processes in deposit and rice soil, which are some special microorganisms, using organic matter
Body, using Fe (III) as only electron acceptor, makes Fe (III) be reduced to Fe (II), and by generation while oxidation of organic compounds
Energy is obtained during thanking supports growth.A kind of sponge iron/sulfate reducing bacteria/iron-reducing bacterium microballoon of the present invention, in anaerobism shape
Under state, sulfate reducing bacteria SRB and iron-reducing bacterium (Comamonas) are attached on the sponge iron for possessing huge specific surface area, sulphur
Hydrochlorate reducing bacteria is by the SO in waste liquid4 2-It is reduced to divalent, the S of generation2-Occur again with the heavy metal Cd (II) in water anti-
It should be combined into sulfide precipitation, the effect of iron-reducing bacterium supplied for electronic not only keeps the reduction activation of sponge iron, while strengthening heavy metal
Reduction process, sponge iron not only owned certain reducing heavy metal ability with high reproducibility, but also system will be made
Dissolved oxygen be maintained under 0.005mg/L, guarantee system be under anaerobic state, from face guarantee sulfate reducing bacteria SRB it is low
Oxidation-reduction potential constitutes a stably and controllable anaerobic reaction system.
The present invention is achieved through the following technical solutions:
The method that sponge iron cooperates with removing sulfate and Cd (II) waste water with microorganism, comprising the following steps:
(1) preparation of sponge ferrous solution
Sponge iron solid is activated with dilute hydrochloric acid, the sponge ferrous solution that preparation concentration is 0.3-0.8g/L is denoted as reaction solution
A；
(2) preparation of sulfate reducing bacteria SRB
It is transferred to 2 rings are selected in desulfovibrio (Desulfovibrio) in desulfovibrio nutrient medium, in 35-37
DEG C it is protected from light 3~5d of culture, 2-3d is expanded culture using desulfovibrio proliferated culture medium with the inoculum concentration of 5-10wt%, is centrifuged
Processing obtains the logarithmic growth phase cell of desulfovibrio, abandons supernatant, bacteria suspension B is made；
(3) preparation of iron-reducing bacterium
2 ring of iron-reduced tuftedmonas (Comamonas) is transferred in iron-reducing bacterium nutrient medium, at 28-30 DEG C
It is protected from light culture 3-5d, 2-3d is expanded culture using iron-reducing bacterium proliferated culture medium with the inoculum concentration of 5-10wt%, at centrifugation
Reason obtains the logarithmic growth phase cell of iron-reducing bacterium, abandons supernatant, bacteria suspension C is made；
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixture
Under anaerobic, reaction solution A, bacteria suspension B and bacteria suspension C are mixed with volume ratio for 1:1:1~1:3:4, it is old
Change 40-60min to be washed with deionized deoxygenated water, impregnated in sterile saline repeatedly after reaction；Obtain sponge iron
With sulfate reducing bacteria/iron-reducing bacterium mixture；
(5) sulfate and Cd (II) purification
Sponge iron obtained by step (4) and sulfate reducing bacteria/iron-reducing bacterium mixture and sulfate and Cd (II) is useless
Water mixes, and reacts 20 hours or more under room temperature, while purifying waste water sulfate and Cd (II).
To further realize the object of the invention, it is preferable that the sponge iron solid is prepared via a method which: with iron cement and
Simple substance carbon dust is raw material, and the mass ratio for controlling simple substance carbon dust and iron cement is 1:1-1:3, under the conditions of temperature is 1100-1300 DEG C
20-25min is calcined to be made.
Preferably, the formula composition of the desulfovibrio nutrient medium are as follows: KH2PO40.6g/L, NH4Cl 1.2g/L,
MgSO4·7H2O 0.2g/L, sodium lactate 3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O
0.3g/L, Na2SO45.5g/L, CaCl2·6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.0-7.5, remaining is water.
Preferably, the formula composition of the desulfovibrio proliferated culture medium are as follows: KH2PO40.8g/L, NH4Cl 1.5g/L,
CaCl2·2H2O 0.3g/L, Na2SO46g/L, MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L,
FeSO4·7H2O 3.0g/L, sodium citrate 0.5g/L adjust pH 7.0-7.5, remaining is water.
Preferably, in step (2), the centrifugal treating is that 3000r/min is centrifuged 10~20min；Bacteria suspension B is protected in 4 DEG C
It deposits；The desulfovibrio (Desulfovibrio) is transferred in 30-40ml desulfovibrio nutrient medium.
Preferably, the iron-reducing bacterium nutrient medium: if taking fresh potato juice dry volume, addition glucose 20~
24g/L, remaining is water；The preparation method of potato juice: removing 160~220 grams of skin fresh potato, be cut into small pieces, add from
Sub- 800~1000mL of water boils 30-35 minutes, filters off potato ball, filtrate is complemented to 1000mL with deionized water.
Preferably, the iron-reducing bacterium proliferated culture medium main component be 2.0~2.5g/L of beef extract, glucose 1.5~
2.5g/L, 5.5~6.0g/L of tryptone, yeast powder 3.0~4.5g/L, pH 6.5~7.5, remaining is water.
Preferably, in step (3), the centrifugal treating is that 3000r/min is centrifuged 10~15min, and bacteria suspension C is protected in 4 DEG C
It deposits；2 ring of iron-reduced tuftedmonas (Comamonas) is transferred in 30-40ml iron-reducing bacterium nutrient medium.
Preferably, the sponge iron impregnated in sterile saline and the mixing of sulfate reducing bacteria/iron-reducing bacterium
Object is placed in refrigerator and is saved at 4 DEG C.
Preferably, control sponge iron and sulfate reducing bacteria/dosage of the iron-reducing bacterium mixture in waste water in step 5)
For 0.5-2g/L；The sulfate and Cd (II) waste water contain the Na of 0.5g/L2SO4；Cd (the NO of 105mg/L3)2Concentration is,
Middle Cd2+Content is 50mg/L, remaining is water.
The present invention is directed to the waste water containing high concentration sulfate and heavy metal Cd (II), and screening is obtained with sulfate Gao Xuan
Selecting property reducing bacteria SRB flora realizes sulfuric acid using synergistic effect between the Anaerobic Corrosion of spongy iron and the sulfate metabolism of SRB
Salt removal synchronous with heavy metal Cd (II).In the present invention, under anaerobic state, sulfate reducing bacteria SRB and iron-reducing bacterium are attached
In on the sponge iron for possessing huge specific surface area, sulfate reducing bacteria is by the SO in waste liquid4 2-It is reduced to divalent, is produced
Raw S2-It reacts again with the heavy metal Cd (II) in water and is combined into sulfide precipitation.The effect of iron-reducing bacterium supplied for electronic is not only protected
The reduction activation of sponge iron is held, while strengthening the reduction process of heavy metal.Sponge iron with high reproducibility is not only owned
Certain reducing heavy metal ability, and it is maintained at the dissolved oxygen of system under 0.005mg/L, guarantee that system is in anaerobism shape
Under state, to guarantee the lower oxidation reduction potential of sulfate reducing bacteria SRB, a stably and controllable anaerobic reaction system is constituted.
(II) indicates the ion price of Cd in Cd (II).
Compared with the existing technology, the advantages of invention and the utility model has the advantages that
1. sponge ferrous-fortifier selected by the present invention is a kind of with large specific surface area, specific surface energy height, stronger electricity
The zeroth order iron material of the superior functions such as chemical enrichment, strong reducing property, physical absorption and flocculation sedimentation, to organic matter in water body, again
The pollutants such as metal and inorganic salts all have good removal capacity, sewage treatment field with development potential.
2. the sulfate reducing bacteria that the present invention selects, can be in an anaerobic environment by sulfate reduction at S2-, with heavy metal Cd
(II) it generates and precipitates and then achieve the purpose that removing heavy metals.Sponge iron has certain adsorption capacity to heavy metal, can facilitate
It captures heavy metal and then is reduced, and Fe (III) can be reduced to Fe (II) by iron-reducing bacterium, Fe's is constant in holding system.
3. equipment needed for the present invention is simple and convenient to operate, reaction is completed at normal temperatures and pressures, and product is solid phase, reactant
System is liquid phase, and product can be easily separated, and therefore, is suitable for large-scale industrial production.
Detailed description of the invention
Fig. 1 is the removal effect figure of metal Cd (II) in embodiment 1-4.
Specific embodiment
The present invention is described in further detail by following embodiment, but the technology contents that are described of the present embodiment be it is illustrative,
Without being restrictive, protection scope of the present invention should not be limited to according to this.
Embodiment 1
A kind of method that sponge iron cooperates with removing sulfate and Cd (II) waste water with microorganism, comprising the following steps:
(1) preparation of sponge iron
Mixed carbon comtent (mass ratio of simple substance carbon dust and iron cement) 1:2,1200 DEG C of reaction temperature, reaction time 25min item
Under part, is calcined by raw material of iron cement, prepare conventional sponge iron solid.It is activated with dilute hydrochloric acid, the sea that preparation concentration is 0.6g/L
Continuous ferrous solution is denoted as reaction solution A.
(2) preparation of sulfate reducing bacteria SRB
From China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.3469) a kind of sulfate reducing bacteria-desulfovibrio (Desulfovibrio bought；Desulfovibrio desulfuricans subspecies) it chooses
2 rings are selected, are transferred into 40ml desulfovibrio nutrient medium, culture 3d is protected from light at 35 DEG C, is used with the inoculum concentration of 5wt%
Desulfovibrio proliferated culture medium expands culture 3d, is centrifuged 10min with 3000r/min, obtains the logarithmic growth of desulfovibrio
Phase cell abandons supernatant, bacteria suspension B is made, and saves in 4 DEG C.
Wherein, desulfovibrio nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L,
Sodium lactate 3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O0.3g/L, Na2SO45.5g/L
CaCl2·6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.2, remaining is water.
Desulfovibrio proliferated culture medium: KH2PO40.8g/L, NH4Cl 1.5g/L, CaCl2·2H2O 0.3g/L,
Na2SO46g/L, MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L, FeSO4·7H2O 3.0g/L,
Sodium citrate 0.5g/L adjusts pH 7.0, remaining is water.
(3) preparation of iron-reducing bacterium
It selects from China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.8048) 2 ring of iron-reduced tuftedmonas (Comamonas) bought, is transferred into 40ml nutrient solution, is protected from light at 28 DEG C
4d is cultivated, 3d is expanded culture using proliferated culture medium with the inoculum concentration of 5wt%, 10min is centrifuged with 3000r/min, is obtained
The logarithmic growth phase cell of iron-reducing bacterium abandons supernatant, bacteria suspension C is made, and saves in 4 DEG C.
Wherein, iron-reduced tuftedmonas nutrient medium is fresh potato juice 800mL, and glucose 22g, remaining is
Water；The preparation method of potato juice: 160 grams of skin fresh potato are removed, is cut into small pieces, deionized water 800mL is added to boil 30 points
Clock filters off potato ball, filtrate is complemented to 800mL with deionized water；
Iron-reduced tuftedmonas proliferated culture medium main component is beef extract 2.0g/L, glucose 1.7g/L, tryptose
Peptone 5.8g/L, yeast powder 3.0g/L, pH 7.4, remaining is water.
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixture
It is under anaerobic after 4:7:9 is thoroughly mixed, to continue with volume ratio by reaction solution A, bacteria suspension B and bacteria suspension C
It is aged 40min, obtains sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixed system, whole process is passed through nitrogen protection and detests
Oxygen environment.
(5) after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion is placed in refrigerator and is saved at 4 DEG C.
Using the waste water of the present embodiment method processing containing sulfate and heavy metal Cd (II): waste water raw material is formulated as being added
Na2SO4Concentration is 0.5g/L, Cd (NO3)2Concentration is 105mg/L (wherein Cd2+Content is 50mg/L), sponge iron/sulphur of addition
Hydrochlorate reducing bacteria/iron-reducing bacterium mixture concentration is 1g/L, remaining is water.In room temperature (at 25 DEG C) reaction, the reaction time is
For 24 hours, it is sampled at interval of 4h, Cd uses Flame Atomic Absorption Spectrometry Determination concentration, as a result as shown in Figure 1.It can from Fig. 1
Out, continue with the reaction time, Cd remaining concentration gradually decreases, its residual concentration only has 4.7mg/L when for 24 hours, i.e., reachable
To 90.6% removal rate.
Embodiment 2
A kind of method that sponge iron cooperates with removing sulfate and Cd (II) waste water with microorganism, comprising the following steps:
(1) preparation of sponge iron
Mixed carbon comtent (mass ratio of simple substance carbon dust and iron cement) 1:2,1200 DEG C of reaction temperature, reaction time 25min item
Under part, is calcined by raw material of iron cement, prepare conventional sponge iron solid.It is activated with dilute hydrochloric acid, the sea that preparation concentration is 0.4g/L
Continuous ferrous solution is denoted as reaction solution A.
(2) preparation of sulfate reducing bacteria SRB
From China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.3469) a kind of sulfate reducing bacteria-desulfovibrio (Desulfovibrio) bought selects 2 rings, is transferred into 40ml
In nutrient solution, it is protected from light culture 5d at 35 DEG C, 2d is expanded culture using proliferated culture medium with the inoculum concentration of 5wt%, with
3000r/min is centrifuged 15min, obtains the logarithmic growth phase cell of desulfovibrio, abandons supernatant, bacteria suspension B is made, and protects in 4 DEG C
It deposits.
Wherein, nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O 0.3g/L, Na2SO45.5g/L, CaCl2·
6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.0, remaining is water.
Proliferated culture medium: KH2PO40.8g/L, NH4Cl 1.5g/L, CaCl2·2H2O 0.3g/L, Na2SO46g/L,
MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate
0.5g/L adjusts pH 7.3, remaining is water.
(3) preparation of iron-reducing bacterium
It selects from China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.8048) 2 ring of iron-reduced tuftedmonas (Comamonas) bought, is transferred into 40ml nutrient solution, is protected from light at 28 DEG C
3d is cultivated, 2d is expanded culture using proliferated culture medium with 5% inoculum concentration, 10min is centrifuged with 3000r/min, obtains iron
The logarithmic growth phase cell of reducing bacteria abandons supernatant, bacteria suspension C is made, and saves in 4 DEG C.
Wherein, the nutrient medium of iron-reducing bacterium is fresh potato juice 1000mL, glucose 20g, remaining is water；Ma Ling
The preparation method of potato juice: removing 160 grams of skin fresh potato, be cut into small pieces, and deionized water 1000mL is added to boil 30 minutes, filters off
Filtrate is complemented to 1000mL with deionized water by potato ball；
The proliferated culture medium main component is beef extract 2.2g/L, glucose 2.5g/L, tryptone 5.5g/L, yeast
Powder 3.5g/L, pH 7.5, remaining is water.
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixed system
It is under anaerobic 5:7:8 with volume ratio by reaction solution A and suspension bacteria liquid B and C, after being thoroughly mixed, continues old
Change 40min, obtains sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixed system, whole process is passed through nitrogen protection anaerobism
Environment.
(5) after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion is placed in refrigerator and is saved at 4 DEG C.
Using the waste water of the present embodiment method processing containing sulfate and heavy metal Cd (II): waste water is formulated as that Na is added2SO4
Concentration is 0.5g/L, Cd (NO3)2Concentration is 105mg/L (wherein Cd2+Content is 50mg/L), sponge iron/sulfate of addition is also
Opportunistic pathogen/iron-reducing bacterium mixture concentration is 1g/L, remaining is water.It is reacted under room temperature (25 DEG C), the reaction time is every for 24 hours
It is sampled every 4h, Cd uses Flame Atomic Absorption Spectrometry Determination concentration.As a result as shown in Figure 1.From figure 1 it appears that with
Reaction time continues, and Cd remaining concentration gradually decreases, its residual concentration only has 7.4mg/L when for 24 hours, that is, can reach 85.2%
Removal rate.
Embodiment 3
A kind of method that sponge iron cooperates with removing sulfate and Cd (II) waste water with microorganism, comprising the following steps:
(1) preparation of sponge iron
Mixed carbon comtent (mass ratio of simple substance carbon dust and iron cement) 1:2,1200 DEG C of reaction temperature, reaction time 25min item
Under part, is calcined by raw material of iron cement, prepare conventional sponge iron solid.It is activated with dilute hydrochloric acid, the sea that preparation concentration is 0.3g/L
Continuous ferrous solution is denoted as reaction solution A.
(2) preparation of sulfate reducing bacteria SRB
From China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.3469) a kind of sulfate reducing bacteria-desulfovibrio bought selects 2 rings, is transferred into 30ml nutrient solution, at 35 DEG C
It is protected from light culture 3d, 2d is expanded culture using proliferated culture medium with 5% inoculum concentration, 10min is centrifuged with 3000r/min, is obtained
The logarithmic growth phase cell of desulfovibrio is obtained, supernatant is abandoned, bacteria suspension B is made, is saved in 4 DEG C.
Wherein, nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O 0.3g/L, Na2SO45.5g/L, CaCl2·
6H2O 0.2g/L, citric acid 0.3g/L adjust pH7.0, remaining is water.
Proliferated culture medium: KH2PO40.8g/L, NH4Cl 1.5g/L, CaCl2·2H2O 0.3g/L, Na2SO46g/L,
MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate
0.5g/L adjusts pH 7.1, remaining is water.
(3) preparation of iron-reducing bacterium
It selects from China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.8048) 2 ring of iron-reduced tuftedmonas bought, is transferred into 40ml nutrient solution, and culture 3d is protected from light at 28 DEG C, with
5% inoculum concentration expands culture 3d using proliferated culture medium, is centrifuged 10min with 3000r/min, obtains pair of iron-reducing bacterium
Number growth period cell, abandons supernatant, bacteria suspension C is made, and saves in 4 DEG C.
Wherein, the nutrient medium of iron-reducing bacterium is fresh potato juice 900mL, glucose 20g, remaining is water；Ma Ling
The preparation method of potato juice: removing 220 grams of skin fresh potato, be cut into small pieces, and deionized water 900mL is added to boil 30 minutes, filters off
Filtrate is complemented to 900mL with deionized water by potato ball.
The proliferated culture medium main component is beef extract 2.4g/L, glucose 2.3g/L, tryptone 5.9g/L, yeast
Powder 4.5g/L, pH 6.5, remaining is water.
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixed system
It is under anaerobic 3:7:10 with volume ratio by reaction solution A and suspension bacteria liquid B and C, after being thoroughly mixed, continues old
Change 40min, obtains sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixed system, whole process is passed through nitrogen protection anaerobism
Environment.
(5) after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion is placed in refrigerator and is saved at 4 DEG C.
Using the waste water of the present embodiment method processing containing sulfate and heavy metal Cd (II): waste water is formulated as that Na is added2SO4
Concentration is 0.5g/L, Cd (NO3)2Concentration is 105mg/L (wherein Cd2+Content is 50mg/L), sponge iron/sulfate of addition is also
Opportunistic pathogen/iron-reducing bacterium mixture concentration is 1g/L, remaining is water.It is reacted under room temperature (25 DEG C), the reaction time is every for 24 hours
It is sampled every 4h, Cd uses Flame Atomic Absorption Spectrometry Determination concentration.As a result as shown in Figure 1.From figure 1 it appears that with
Reaction time continues, and Cd remaining concentration gradually decreases, its residual concentration only has 4.2mg/L when for 24 hours, that is, can reach 91.6%
Removal rate.
Embodiment 4
A kind of method that sponge iron cooperates with removing sulfate and Cd (II) waste water with microorganism, comprising the following steps:
(1) preparation of sponge iron
Mixed carbon comtent (mass ratio of simple substance carbon dust and iron cement) 1:2,1200 DEG C of reaction temperature, reaction time 25min item
Under part, is calcined by raw material of iron cement, prepare conventional sponge iron solid.It is activated with dilute hydrochloric acid, the sea that preparation concentration is 0.7g/L
Continuous ferrous solution is denoted as reaction solution A.
(2) preparation of sulfate reducing bacteria SRB
From China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.3469) 2 rings are selected in a kind of sulfate reducing bacteria-desulfovibrio bought, be transferred into 30ml nutrient solution, 35
It DEG C is protected from light culture 4d, 2d is expanded culture using proliferated culture medium with 5% inoculum concentration, 10min is centrifuged with 3000r/min,
The logarithmic growth phase cell of desulfovibrio is obtained, supernatant is abandoned, bacteria suspension B is made, is saved in 4 DEG C.
Wherein, nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leach cream 1.2g/L, CaSO41.6g/L, FeSO4·7H2O 0.3g/L, Na2SO45.5g/L, CaCl2·
6H2O 0.2g/L, citric acid 0.3g/L adjust pH 7.0, remaining is water.
Proliferated culture medium: KH2PO40.8g/L, NH4Cl 1.5g/L, CaCl2·2H2O 0.3g/L, Na2SO46g/L,
MgSO4·7H2O 0.6g/L, sodium lactate 4.8g/L, yeast leach cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate
0.5g/L adjusts pH7.3, remaining is water.
(3) preparation of iron-reducing bacterium
It selects from China General Microbiological culture presevation administrative center (city, BeiJing, China Chaoyang District, postcode 100101, number
1.8048) 2 ring of iron-reduced tuftedmonas bought, is transferred into 40ml nutrient solution, and culture 5d is protected from light at 28 DEG C, with
5% inoculum concentration expands culture 2d using proliferated culture medium, is centrifuged 12min with 3000r/min, obtains pair of iron-reducing bacterium
Number growth period cell, abandons supernatant, bacteria suspension C is made, and saves in 4 DEG C.
Wherein, the nutrient medium of iron-reducing bacterium is fresh potato juice 1000mL, glucose 20g, remaining is water；Ma Ling
The preparation method of potato juice: removing 220 grams of skin fresh potato, be cut into small pieces, and deionized water 1000mL is added to boil 30 minutes, filters off
Filtrate is complemented to 1000mL with deionized water by potato ball；
The proliferated culture medium main component is beef extract 2.2g/L, glucose 2.2g/L, tryptone 6.0g/L, yeast
Powder 3.5g/L, pH 7.5, remaining is water.
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixed system
It is under anaerobic 6:7:7 with volume ratio by reaction solution A and suspension bacteria liquid B and C, after being thoroughly mixed, continues old
Change 40min, obtains sponge iron and sulfate reducing bacteria/iron-reducing bacterium mixed system, whole process is passed through nitrogen protection anaerobism
Environment.
(5) after reaction, with deionized deoxygenated water cleansing sponge iron/microbe microsphere repeatedly, in sterile saline
Middle immersion is placed in refrigerator and is saved at 4 DEG C.
Handle the waste water of containing sulfate and heavy metal Cd (II): the raw material of waste water is formulated as that Na is added2SO4Concentration is 0.5g/
L, Cd (NO3)2Concentration is 105mg/L (wherein Cd2+Content is 50mg/L), sponge iron/sulfate reducing bacteria/iron reduction of addition
Bacterium mixture concentration is 1g/L, remaining is water.It is reacted under room temperature (25 DEG C), the reaction time is for 24 hours, to sample at interval of 4h, Cd
Using Flame Atomic Absorption Spectrometry Determination concentration.As a result as shown in Figure 1, it can be seen from the figure that holding with the reaction time
Continuous, Cd remaining concentration gradually decreases, its residual concentration only has 6.9mg/L when for 24 hours, that is, can reach 86.2% removal rate.
In the present invention, SRB Biology-iron Anaerobic Biotechnology combines in such a way that sponge iron electronation is strengthened, and makes sulphur
Hydrochlorate reducing bacteria (SRB) is in a kind of active state, and organic matter, which is digested to decompose by anaerobe, generates electronics, also for sulfate
Opportunistic pathogen provides electronics, so that sulfate reduction is sulfide by sulfate reducing bacteria.While the generation of sulfide, also and in water
Micro heavy Cd (II) react and generate sulfide precipitation, do not remove only Cd remaining in water (II), and consume
H2S prevents it from overflowing and getting into the air from water, generates threat to the life of staff.It can be seen that sponge iron substrate
It is added, increases the activity of sulfate reducing bacteria SRB, the maximum sulphur removal potential of SRB can be facilitated out.
The advanced research of common SRB depollution object technology be based primarily upon electrochemistry in terms of research, such as Harbin industry
Anaerobism suspension growth reactor is studied to the removal effect of sulfate and ammonia nitrogen, within the residence time of 3d, sulphur in the sea university Zheng Huan
Acid group, ammonia nitrogen removal frank have only reached 69%, 58%, by 31 bacterial strains isolated, discovery removing sulfate radical and except deammoniation
Nitrogen is in the coefficient result of various bacteria.Under the invigoration effect of electric field, expand cathodic process, so that the effect that desulfurization is denitrogenated
Fruit is promoted.The Li Guanghe seminar of Tsinghua University studies electric field-enhanced research sulfate reducing bacteria and goes to create sulfate process, hair
Now as I≤1.50mA, with the increase of electric current, the sulfate reduction rate increases, and optimum current intensity is 1.50mA, average to go back
Former rate is 28.3~35.3mg/d.Compared to these electrochemical research, the present invention uses sponge iron SRB anaerobic reduction system not
Energy consumption, and treatment effeciency are only reduced, engineering practical operation is simple.
According to the report that heavy metals Cd (II) is handled, under conditions of initial concentration is 50mg/L, action time is
12h, sponge iron can reach 83.26% to the removal rate of Cd (II), and (Bi Na and its removes cadmium performance study at the preparation of sphere sponge iron
[J], HBLG08-015).Under conditions of initial concentration is 40mg/L, after acting on 7d, sulfate reducing bacteria goes Cd (II)
Except rate is up to 66% (the separation identification of Liu Yan, Dang Zhi, one strain of sulfate reduction bacteria-Desulfovibriosp.strainSRBa-
And its removal Cadmium In The Water Body ion research [J]), comparison diagram 1, it can be seen that pass through sponge iron/sulfate reducing bacteria/iron-reducing bacterium
Microballoon invigoration effect, initial concentration be 50mg/L, action time be 1d after, to Cd (II) metal in embodiment 1-4
Removal rate has respectively reached 90.6%, 85.2%, 91.6% and 86.2%, is above sponge iron and sulfate reducing bacteria is individually made
The removal efficiency of used time, show the invention be for the removal of the formation of microballoon and heavy metal Cd (II) it is effectively, a huge sum of money
Belong to and having a good application prospect in wastewater treatment.
Embodiment of the present invention are not limited by the above embodiments, other any real without departing from spirit of the invention
Made changes, modifications, substitutions, combinations, simplifications under matter and principle, should be equivalent substitute mode, are included in the present invention
Protection scope within.
Claims (10)
1. sponge iron cooperates with removing sulfate and Cd with microorganism2+The method of waste water, it is characterised in that the following steps are included:
(1) preparation of sponge ferrous solution
Sponge iron solid is activated with dilute hydrochloric acid, the sponge ferrous solution that preparation concentration is 0.3-0.8g/L is denoted as reaction solution A；
(2) preparation of sulfate reducing bacteria SRB
It is transferred to 2 rings are selected in desulfovibrio (Desulfovibrio) in desulfovibrio nutrient medium, is kept away at 35-37 DEG C
3~5d of optical culture expands culture 2-3d using desulfovibrio proliferated culture medium with the inoculum concentration of 5-10wt%, centrifugal treating,
The logarithmic growth phase cell of desulfovibrio is obtained, supernatant is abandoned, bacteria suspension B is made；
(3) preparation of iron-reducing bacterium
2 ring of iron-reduced tuftedmonas (Comamonas) is transferred in iron-reducing bacterium nutrient medium, is protected from light at 28-30 DEG C
3-5d is cultivated, 2-3d is expanded culture using iron-reducing bacterium proliferated culture medium with the inoculum concentration of 5-10wt%, centrifugal treating obtains
The logarithmic growth phase cell of iron-reducing bacterium is obtained, supernatant is abandoned, bacteria suspension C is made；
(4) sponge iron and the preparation of sulfate reducing bacteria/iron-reducing bacterium mixture
Under anaerobic, reaction solution A, bacteria suspension B and bacteria suspension C are mixed with volume ratio for 1:1:1~1:3:4, is aged 40-
60min is washed repeatedly with deionized deoxygenated water, is impregnated in sterile saline after reaction；Obtain sponge iron and sulfuric acid
Salt reducing bacteria/iron-reducing bacterium mixture；
(5) sulfate and Cd2+Purification
By sponge iron obtained by step (4) and sulfate reducing bacteria/iron-reducing bacterium mixture and sulfate and Cd2+Waste water mixing,
It is reacted 20 hours or more under room temperature, while purifying waste water sulfate and Cd2+。
2. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature exist
In the sponge iron solid is prepared via a method which: using iron cement and simple substance carbon dust as raw material, controlling simple substance carbon dust and iron cement
Mass ratio is 1:1-1:3, and calcining 20-25min is made under the conditions of temperature is 1100-1300 DEG C.
3. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature exist
In the formula composition of the desulfovibrio nutrient medium are as follows: KH2PO4 0.6 g/L, NH4Cl 1.2g/L, MgSO4·
7H20.2 g of O/L, sodium lactate 3.22g/L, yeast leach 1.2 g of cream/L, CaSO41. 6 g/L, FeSO4·7H2O
0. 3 g/L, Na2SO45. 5 g/L, CaCl2·6H20.2 g of O/L, 0. 3 g of citric acid/L adjust pH 7.0-7.5,
Remaining is water.
4. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature exist
In the formula composition of the desulfovibrio proliferated culture medium are as follows: KH2PO40.8 g/L, NH4Cl 1.5g/L, CaCl2·2H2O
0.3 g/L, Na2SO46g/L, MgSO4·7H2O 0. 6g/L, sodium lactate 4.8g/L, yeast leaching 3. 5g/L of cream,
FeSO4·7H23.0 g of O/L, sodium citrate 0.5g/L adjust pH 7.0-7.5, remaining is water.
5. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature exist
In in step (2), the centrifugal treating is that 3000 r/min are centrifuged 10~20 min；Bacteria suspension B is saved in 4 DEG C；The desulfurization
Vibrios (Desulfovibrio) is transferred in 30-40ml desulfovibrio nutrient medium.
6. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature exist
In the iron-reducing bacterium nutrient medium: if taking fresh potato juice dry volume, 20~24g/L of glucose is added, remaining is
Water；The preparation method of potato juice: 160~220 grams of skin fresh potato are removed, is cut into small pieces, deionized water 800~1000 is added
ML boils 30-35 minutes, filters off potato ball, filtrate is complemented to 1000 mL with deionized water.
7. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature exist
In the iron-reducing bacterium proliferated culture medium main component is 2.0~2.5 g/L of beef extract, 1.5~2.5 g/L of glucose, pancreas egg
White 5.5~6.0 g/L of peptone, yeast powder 3.0~4.5 g/L, pH 6.5~7.5, remaining is water.
8. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature exist
In in step (3), the centrifugal treating is that 3000 r/min are centrifuged 10~15 min, and bacteria suspension C is saved in 4 DEG C；The iron is also
Former 2 ring of comamonas (Comamonas) is transferred in 30-40ml iron-reducing bacterium nutrient medium.
9. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature exist
In the sponge iron impregnated in sterile saline and sulfate reducing bacteria/iron-reducing bacterium mixture are placed 4 in refrigerator
It is saved at DEG C.
10. sponge iron according to claim 1 cooperates with removing sulfate and Cd with microorganism2+The method of waste water, feature
It is, sponge iron is controlled in step 5) and sulfate reducing bacteria/dosage of the iron-reducing bacterium mixture in waste water is 0.5-2g/L；
The sulfate and Cd2+Waste water contains the Na of 0.5g/L2SO4, 105mg/L Cd (NO3)2。
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