CN106115931A - Sponge iron is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water - Google Patents
Sponge iron is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water Download PDFInfo
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- CN106115931A CN106115931A CN201610508395.5A CN201610508395A CN106115931A CN 106115931 A CN106115931 A CN 106115931A CN 201610508395 A CN201610508395 A CN 201610508395A CN 106115931 A CN106115931 A CN 106115931A
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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
Abstract
The invention discloses sponge iron and microorganism is worked in coordination with and gone removing sulfate and the method for Cd (II) waste water；The method is under anaerobic, by the bacteria suspension C of sponge iron solution A, the bacteria suspension B of sulfate reducting bacteria and iron-reduced tuftedmonas, with volume ratio as 1:1:1～1:3:4 mixes, it is aged 40 60min, after reaction terminates, use deionized deoxygenated water cyclic washing, soak in physiological saline solution；Obtain the mixture of sponge iron and sulfate reducting bacteria/iron-reducing bacterium；Gained sponge iron mixes with sulfate and Cd (II) waste water with the mixture of sulfate reducting bacteria/iron-reducing bacterium, reacts more than 20 hours, purify waste water sulfate and Cd (II) simultaneously under room temperature.The present invention reaches more than 85% to the clearance of Cd (II) metal, and equipment needed thereby is simple and convenient to operate, and reaction completes at normal temperatures and pressures, and product is solid phase, and reaction system is liquid phase, and product can be easily separated, it is adaptable to large-scale industrial produces.
Description
Technical field
The method that the present invention relates to advanced treatment of wastewater, specifically processes containing sulfate and heavy metal Cd (II) concentration
The deep treatment method of the sewage exceeded standard.
Background technology
Cadmium wastewater is acknowledged as one of public hazards of current serious harm environment.The pollution of Cadmium In The Water Body essentially from
Rainwash and industrial wastewater.In sulphur iron ore extracting sulfuric acid and the waste water discharged when being produced phosphate fertilizer by rock phosphate in powder higher containing cadmium,
Every liter of waste water containing cadmium up to tens of to hundreds of micrograms, Pb-Zn deposits in air and non-ferrous metal metallurgy, burning, plastic
Burn the cadmium granule formed all possibly in water；The catalyst of raw material, pigment, stabilizer for plastics, synthetic rubber sulfuration is made with pot
Water body also can be polluted by the cadmium of the discharge such as agent, antibacterial, during urban water, often due to container and the dirt of pipeline
Dye also can make cadmium content in drinking water increase.The discharge of industrial wastewater makes the cadmium content in coastal seawater and plankton body be higher than
Off-lying sea, the cadmium content of industrial occupancy surface water is higher than non-industrial occupancy.Become environmental pollution, such as waste Ni-Cd battery.
Cadmium, to the pollution that first pollution of environment is to soil and water body, then leads to corn, vegetable, domestic animal and poultry
Cadmium pollution, finally enters human body, causes human body to be poisoned.The murder by poisoning of cadmium maximum is that its meeting be accumulated by food chain, richness is amassed, with
Cause to directly act on human body and cause serious disease or promote the generation of chronic disease.After cadmium poisoning, mainly show as kidney function
Obstacle, osteoporosis and softening, gnawing pains take no rest all day to make people feel, the nuisance disease Itai-itai diseases of nineteen sixty-eight Japan's discovery, just
It is the prominent example of cadmium poisoning, also occurs in that the situation of contaminated area cadmium poisoning in China.
In " water environment quality standard " (GB3838-2002) that within 2002, promulgate, the cadmium content in regulation I class water must
Must be less than 0.001mg L-1, the cadmium content in II～IV class water have to be lower than 0.005mg L-1, the cadmium content in V class water is not
More than 0.01mg L-1." agricultural irrigation water quality standard " (GB 5084-92) regulation cadmium content have to be lower than 0.005mg L-1。
The highest permission concentration of emission of " integrated wastewater discharge standard " (GB 8978-1996) total cadmium of regulation pollutant is 0.1mg L-1。
" sewage enters municipal sewage system water standard " (CJ 3082-1999) regulation sewage enters cadmium in municipal sewage system pollutant
The highest permission concentration of emission is 0.1mg L-1。
Cadmium causes the attention of countries in the world to the murder by poisoning of human body, and China national environmental law specifies, cadmium is first kinds of pollution matter,
The most handy dilution method replaces necessary process.And the concentration of the cadmium wastewater cadmium before treatment of general factory is all far above state's domestic discipline and family rules
(the highest permissible discharge concentration of cadmium in industrial wastewater is 0.1mg L to fixed standard-1), so cadmium wastewater is the most necessary
Process, carry out qualified discharge, containing also must properly stack every refuse, in order to avoid rain drop erosion, cause soil, water pollution.
Currently for cadmium wastewater, main removal technology has physical-chemical process, absorption method and bioanalysis etc..Wherein, heavy
Shallow lake method advantage is that nertralizer is cheap, and technique is simple, and sediment water content is low, and shortcoming is that sediment weight is big, goes out the water hardness high, reaction
Speed is relatively slow, and the sediment stacked can cause secondary pollution.Ferrum oxidizing process technical process is simple, and treatment conditions are gentle, but administers
Effect obvious compound use face is narrower, is generally used for processing specific sewage, and the problem that the most many technical combinations are brought.Drift
The effective scope of application of white lead oxidative treatment is narrow, and shortcoming is to be only applicable to containing cyanogen, the electroplating wastewater of cadmium, and the waste residue Han cadmium
Process be also the problem required study.Electrolysis cadmium clearance is high, and recoverable is widely used in the improvement of waste water, but
Cost is higher, the most concentrated after be electrolysed better economic benefit again, limit the application of electrolysis.Absorption method removes effect
Fruit is good, but control condition is the most, and practical operation is difficult.Ion-exchange purification degree is high, can reclaim cadmium, dirty without secondary
Dye, but there is also relatively costly problem.Membrane separation process clearance is high, can reclaim the cadmium salt in waste water, and technique is simple, but film
Selectivity ratios higher, different waste water must study matched film, the composition of waste water also must more stable,
Membrane module designs is difficult, invests the highest.Bioremediation technology low cost, efficiency is high, easily operates, does not has secondary pollution, so
And there is the microorganism of special degradation capability kind in the environment, negligible amounts, it is in a disadvantageous position in interspecies competition simultaneously.Raw
Thing reinforcement technique has the advantage of bioremediation technology, good development prospect, but fixation support cost is high, service life is short.
As a kind of novel Zero-valent Iron material, sponge iron shows stronger place during processing water pollutant
Reason ability.Relative to other Zero-valent Iron material, iron filings and iron powder need secondary rust removal, and specific surface area is little, there is secondary dirty
The defect that dye is low with removal efficiency, nanometer iron powder preparation cost is higher, it is easy to secondary oxidation, has potential environment and biology poison
Property.It is heavy that sponge iron has specific surface area is big, specific surface energy is high, stronger electrochemistry enrichment, strong reducing property, physical absorption and flocculation
The superior physical and chemical performances such as shallow lake.Owing to sponge iron main component is ferrum, its loose porous internal structure, it is provided that ratio table
Area is 5-10 times of common iron filings, can make the oxygen in water, with ferrum, oxidation reaction the most thoroughly occur, and logical filtering type is except shallow lake side
Formula is got rid of, to pipeline, boiler recirculated water dissolved oxygen corrosion, after treatment water dissolution oxygen content can reach 0.005mg/L with
Under, can reinforced anaerobic process effectively.The pollutant such as Organic substance, heavy metal and inorganic salt in water body are all had very well by sponge iron
Removal capacity, be the Zero-valent Iron material of a class great potential.It is reported, sponge iron and microorganism form a kind of immobilization biological
System, at optimum conditions, water outlet TP can be down to below 0.5mg/L, and (Zhang Lidong, sponge iron mutually rush collaborative with microorganism dephosphorization is ground
Study carefully [J]).When pH value is 5, reacting 1h, sponge iron can reach 0.30mg/g (Gu Yingying, spongy iron reducing water to nitrate reduction
The preliminary study [J] of middle nitrate).And for heavy metal, under certain initial concentration, optimal pH, temperature and particle diameter, sponge
Cr (VI) is gone decapacitation to reach 0.18mg/g (Sun Yingxue, sponge iron processes Cr kinetics [J]) by ferrum.
Sulfate reducting bacteria (SRB) processes heavy metal wastewater thereby, is the S utilizing SRB under anaerobic to produce2-With in waste water
Heavy metal ion reaction, generate metal sulfide precipitation with heavy-metal ion removal, SRB pure culture processing method exists and separates
The problems such as it is big that Purification is numerous and diverse, operating condition is harsh, strain runs off.And anaerobic sludge method can provide mud to carry for SRB strain
Body, forms a metastable environment.But common anaerobic sludge flocculation structure is loose, and settling property is poor, unit microorganism
Content is few, and activity is the highest, there is also the problem that strain runs off.Therefore, it is necessary to SRB strain sludge immobilization to be processed a huge sum of money
Belong to waste water.
Summary of the invention
Present invention aim at providing a kind of and play sponge iron, sulfate reducting bacteria and iron-reducing bacterium coordinated effect,
The clearance of Cd (II) metal is reached more than 85%, is significantly higher than removal when sponge iron and sulfate reducting bacteria independent role
Efficiency, and the sponge iron that makes heavy metal in waste water Cd (II) and sulfate synchronize to remove collaborative with microorganism go removing sulfate and
The method of Cd (II) waste water.
Ferrum also pathogenic microorganism is often referred to the microorganism with dissimilatory reduction Fe (III) function.Alienation Fe (III) reduction is anaerobism
One of Biochemical processes important in deposit and rice soil, are that some special microorganisms utilize Organic substance to supply for electronics
Body, while oxidation of organic compounds, using Fe (III) as only electron acceptor, makes Fe (III) be reduced to Fe (II), and by generation
Energy support growth is obtained during thanking.One sponge iron/sulfate reducting bacteria/iron-reducing bacterium microsphere of the present invention, at anaerobism shape
Under state, sulfate reducting bacteria SRB and iron-reducing bacterium (Comamonas) are attached to have on the sponge iron of huge specific surface area, sulfur
Hydrochlorate reducing bacteria is by the SO in waste liquid4 2-It is reduced to divalent, the S of generation2-Occur anti-again with the heavy metal Cd (II) in water
Should be combined into sulfide precipitation, iron-reducing bacterium supplied for electronic effect not only keeps the reducing activity of sponge iron, strengthens heavy metal simultaneously
Reduction process, there is the most owned certain reducing heavy metal ability of sponge iron of high reproducibility, and system will be made
Dissolved oxygen be maintained under 0.005mg/L, it is ensured that system is under anaerobic state, from face ensure sulfate reducting bacteria SRB low
Oxidation-reduction potential, constitutes one and stablizes controlled anaerobic reaction system.
The present invention is achieved through the following technical solutions:
Sponge iron is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, comprises the following steps:
(1) preparation of sponge iron solution
Being activated by sponge iron solid dilute hydrochloric acid, preparation concentration is the sponge iron solution of 0.3-0.8g/L, is designated as reactant liquor
A；
(2) preparation of sulfate reducting bacteria SRB
Transfer in desulfovibrio Nutrient medium, at 35-37 by desulfovibrio (Desulfovibrio) selects 2 rings
DEG C lucifuge cultivates 3～5d, uses desulfovibrio proliferated culture medium to be enlarged cultivating 2-3d with the inoculum concentration of 5-10wt%, centrifugal
Process, it is thus achieved that the exponential phase cell of desulfovibrio, abandon supernatant, make bacteria suspension B；
(3) preparation of iron-reducing bacterium
Iron-reduced tuftedmonas (Comamonas) 2 ring is transferred in iron-reducing bacterium Nutrient medium, at 28-30 DEG C
Lucifuge cultivates 3-5d, uses iron-reducing bacterium proliferated culture medium to be enlarged cultivating 2-3d, centrifugal place with the inoculum concentration of 5-10wt%
Reason, it is thus achieved that the exponential phase cell of iron-reducing bacterium, abandons supernatant, makes bacteria suspension C；
(4) sponge iron and the preparation of sulfate reducting bacteria/iron-reducing bacterium mixture
Under anaerobic, by reactant liquor A, bacteria suspension B and bacteria suspension C, with volume ratio as 1:1:1～1:3:4 mixes, old
Change 40-60min, after reaction terminates, use deionized deoxygenated water cyclic washing, soak in physiological saline solution；Obtain sponge iron
Mixture with sulfate reducting bacteria/iron-reducing bacterium；
(5) sulfate and Cd (II) purify
The mixture of step (4) gained sponge iron with sulfate reducting bacteria/iron-reducing bacterium is given up with sulfate and Cd (II)
Water mixes, and reacts more than 20 hours, purify waste water sulfate and Cd (II) simultaneously under room temperature.
For realizing the object of the invention further, it is preferable that described sponge iron solid is prepared via a method which: with iron cement and
Simple substance carbon dust is raw material, and the mass ratio controlling simple substance carbon dust and iron cement is 1:1-1:3, under the conditions of temperature is 1100-1300 DEG C
Calcining 20-25min prepares.
Preferably, the formula of described desulfovibrio Nutrient medium consists of: KH2PO40.6g/L, NH4Cl 1.2g/L,
MgSO4·7H2O 0.2g/L, sodium lactate 3.22g/L, yeast leaches 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, and remaining is water.
Preferably, the formula of described desulfovibrio proliferated culture medium consists of: 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 leaches cream 3.5g/L,
FeSO4·7H2O 3.0g/L, sodium citrate 0.5g/L, adjust pH 7.0-7.5, and remaining is water.
Preferably, in step (2), described centrifugal treating is that 3000r/min is centrifuged 10～20min；Bacteria suspension B is in 4 DEG C of guarantors
Deposit；Described desulfovibrio (Desulfovibrio) is transferred in 30-40ml desulfovibrio Nutrient medium.
Preferably, described iron-reducing bacterium Nutrient medium: if taking fresh potato juice dry volume, add glucose 20～
24g/L, remaining is water；The preparation method of potato juice: remove skin fresh potato 160～220 grams, be cut into small pieces, add from
Sub-water 800～1000mL boils 30-35 minute, filters off potato ball, with deionized water, filtrate is complemented to 1000mL.
Preferably, described iron-reducing bacterium proliferated culture medium is mainly composed of Carnis Bovis seu Bubali cream 2.0～2.5g/L, glucose 1.5～
2.5g/L, tryptone 5.5～6.0g/L, yeast powder 3.0～4.5g/L, pH 6.5～7.5, remaining is water.
Preferably, in step (3), described centrifugal treating is that 3000r/min is centrifuged 10～15min, and bacteria suspension C is in 4 DEG C of guarantors
Deposit；Described iron-reduced tuftedmonas (Comamonas) 2 ring is transferred in 30-40ml iron-reducing bacterium Nutrient medium.
Preferably, the described sponge iron soaked in physiological saline solution and the mixing of sulfate reducting bacteria/iron-reducing bacterium
Thing is placed in refrigerator and is preserved at 4 DEG C.
Preferably, step 5) in control sponge iron and sulfate reducting bacteria/iron-reducing bacterium mixture consumption in waste water
For 0.5-2g/L；Described sulfate and Cd (II) waste water contain the Na of 0.5g/L2SO4；Cd (the NO of 105mg/L3)2Concentration is, its
Middle Cd2+Content is 50mg/L, and remaining is water.
The present invention is directed to containing high concentration sulfate and the waste water of heavy metal Cd (II), screening obtains having sulfate Gao Xuan
Selecting property reducing bacteria SRB flora, utilizes cooperative effect between the Anaerobic Corrosion of spongy iron and the sulfate metabolism of SRB, it is achieved sulphuric acid
The synchronization of salt and heavy metal Cd (II) is removed.In the present invention, under anaerobic state, sulfate reducting bacteria SRB and iron-reducing bacterium are attached
On the sponge iron having huge specific surface area, sulfate reducting bacteria is by the SO in waste liquid4 2-It is reduced to divalent, produces
Raw S2-React with the heavy metal Cd (II) in water again and be combined into sulfide precipitation.Iron-reducing bacterium supplied for electronic effect is not only protected
Hold the reducing activity of sponge iron, strengthen the reduction process of heavy metal simultaneously.The sponge iron with high reproducibility is the most owned
Certain reducing heavy metal ability, and the dissolved oxygen making system is maintained under 0.005mg/L, it is ensured that system is in anaerobism shape
Under state, thus ensure the lower oxidation reduction potential of sulfate reducting bacteria SRB, constitute one and stablize controlled anaerobic reaction system.
In Cd (II), (II) represents the ion price of Cd.
Relative to prior art, the advantage of invention and beneficial effect:
1. the sponge iron hardening agent selected by the present invention, is a kind of to have the electricity that specific surface area is big, specific surface energy is high, stronger
The Zero-valent Iron material of the superior functions such as chemical enrichment, strong reducing property, physical absorption and flocculation sediment, to Organic substance, weight in water body
The pollutant such as metal and inorganic salt all have good removal capacity, in the great development potentiality of sewage treatment area.
2. the sulfate reducting bacteria that the present invention selects, can become S by sulfate reduction in anaerobic environment2-, with heavy metal Cd
(II) generate precipitation and then reach the purpose of removing heavy metals.Sponge iron heavy metal has certain absorbability, it is possible to convenient
Catching heavy metal and then be reduced, and Fe (III) can be reduced to Fe (II) by iron-reducing bacterium, in holding system, Fe's is constant.
Equipment needed thereby the most of the present invention is simple and convenient to operate, and reaction completes at normal temperatures and pressures, and product is solid phase, reactant
System is liquid phase, and product can be easily separated, therefore, it is adaptable to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the removal effect figure of metal Cd (II) in embodiment 1-4.
Detailed description of the invention
The present invention is described in further detail by following example, but the technology contents that the present embodiment is described is illustrative,
Rather than determinate, should not limit to protection scope of the present invention according to this.
Embodiment 1
A kind of sponge iron is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, comprises the following steps:
(1) preparation of sponge iron
At mixed carbon comtent (simple substance carbon dust and the mass ratio of iron cement) 1:2, reaction temperature 1200 DEG C, the bar of response time 25min
Under part, calcine with ferrum mud as a raw material, the sponge iron solid that preparation is conventional.Activating with dilute hydrochloric acid, preparation concentration is the sea of 0.6g/L
Continuous ferrous solution, is designated as reactant liquor A.
(2) preparation of sulfate reducting bacteria SRB
From General Microbiological Culture preservation administrative center of China (Chaoyang District, city of BeiJing, China, postcode 100101, numbering
1.3469) a kind of sulfate reducting bacteria desulfovibrio (Desulfovibrio bought；Desulfovibrio desulfuricans subspecies) choose
Select 2 rings, be transferred in 40ml desulfovibrio Nutrient medium, cultivate 3d 35 DEG C of lucifuges, use with the inoculum concentration of 5wt%
Desulfovibrio proliferated culture medium is enlarged cultivating 3d, is centrifuged 10min with 3000r/min, it is thus achieved that the logarithmic growth of desulfovibrio
Phase cell, abandons supernatant, makes bacteria suspension B, in 4 DEG C of preservations.
Wherein, desulfovibrio Nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L,
Sodium lactate 3.22g/L, yeast leaches 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, and 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 leaches cream 3.5g/L, FeSO4·7H2O 3.0g/L,
Sodium citrate 0.5g/L, adjusts pH 7.0, and remaining is water.
(3) preparation of iron-reducing bacterium
Select from General Microbiological Culture preservation administrative center of China (Chaoyang District, city of BeiJing, China, postcode 100101, numbering
1.8048) iron-reduced tuftedmonas (Comamonas) 2 ring bought, it is transferred in 40ml nutritional solution, 28 DEG C of lucifuges
Cultivate 4d, use proliferated culture medium to be enlarged cultivating 3d with the inoculum concentration of 5wt%, be centrifuged 10min with 3000r/min, it is thus achieved that
The exponential phase cell of iron-reducing bacterium, abandons supernatant, makes bacteria suspension C, in 4 DEG C of preservations.
Wherein, iron-reduced tuftedmonas Nutrient medium is fresh potato juice 800mL, glucose 22g, and remaining is
Water；The preparation method of potato juice: remove skin fresh potato 160 grams, be cut into small pieces, adds deionized water 800mL and boils 30 points
Clock, filters off potato ball, with deionized water, filtrate is complemented to 800mL；
Iron-reduced tuftedmonas proliferated culture medium is mainly composed of Carnis Bovis seu Bubali cream 2.0g/L, glucose 1.7g/L, Trypsin
Peptone 5.8g/L, yeast powder 3.0g/L, pH 7.4, remaining is water.
(4) sponge iron and the preparation of sulfate reducting bacteria/iron-reducing bacterium mixture
After under anaerobic reactant liquor A, bacteria suspension B and bacteria suspension C being thoroughly mixed with volume ratio for 4:7:9, continue
Ageing 40min, obtains the mixed system of sponge iron and sulfate reducting bacteria/iron-reducing bacterium, and whole process is passed through nitrogen protection and detests
Oxygen environment.
(5) after reaction terminates, with deionized deoxygenated water cyclic washing sponge iron/microbe microsphere, at physiological saline solution
Middle immersion, places in refrigerator and preserves at 4 DEG C.
The present embodiment method is used to process containing sulfate and the waste water of heavy metal Cd (II): waste water preparation of raw material is for adding
Na2SO4Concentration is 0.5g/L, Cd (NO3)2Concentration is 105mg/L (wherein Cd2+Content is 50mg/L), the sponge iron/sulfur of addition
Hydrochlorate reducing bacteria/iron-reducing bacterium mixture concentration is 1g/L, and remaining is water.In room temperature (at 25 DEG C) reaction, the response time is
24h, samples at interval of 4h, and Cd uses Flame Atomic Absorption Spectrometry Determination concentration, and result is as shown in Figure 1.Can from Fig. 1
Going out, along with continuing of response time, Cd remaining concentration gradually decreases, and when 24h, its residual concentration only has 4.7mg/L, i.e. up to
To the clearance of 90.6%.
Embodiment 2
A kind of sponge iron is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, comprises the following steps:
(1) preparation of sponge iron
At mixed carbon comtent (simple substance carbon dust and the mass ratio of iron cement) 1:2, reaction temperature 1200 DEG C, the bar of response time 25min
Under part, calcine with ferrum mud as a raw material, the sponge iron solid that preparation is conventional.Activating with dilute hydrochloric acid, preparation concentration is the sea of 0.4g/L
Continuous ferrous solution, is designated as reactant liquor A.
(2) preparation of sulfate reducting bacteria SRB
From General Microbiological Culture preservation administrative center of China (Chaoyang District, city of BeiJing, China, postcode 100101, numbering
1.3469) a kind of sulfate reducting bacteria desulfovibrio (Desulfovibrio) bought selects 2 rings, is transferred into 40ml
In nutritional solution, cultivate 5d 35 DEG C of lucifuges, use proliferated culture medium to be enlarged cultivating 2d with the inoculum concentration of 5wt%, with
3000r/min is centrifuged 15min, it is thus achieved that the exponential phase cell of desulfovibrio, abandons supernatant, makes bacteria suspension B, in 4 DEG C of guarantors
Deposit.
Wherein, Nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leaches 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, and 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 leaches cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate
0.5g/L, adjusts pH 7.3, and remaining is water.
(3) preparation of iron-reducing bacterium
Select from General Microbiological Culture preservation administrative center of China (Chaoyang District, city of BeiJing, China, postcode 100101, numbering
1.8048) iron-reduced tuftedmonas (Comamonas) 2 ring bought, is transferred in 40ml nutritional solution, 28 DEG C of lucifuges
Cultivating 3d, the inoculum concentration with 5% uses proliferated culture medium to be enlarged cultivating 2d, is centrifuged 10min with 3000r/min, it is thus achieved that ferrum
The exponential phase cell of reducing bacteria, abandons supernatant, makes bacteria suspension C, in 4 DEG C of preservations.
Wherein, the Nutrient medium of iron-reducing bacterium is fresh potato juice 1000mL, glucose 20g, and remaining is water；Ma Ling
The preparation method of potato juice: remove skin fresh potato 160 grams, be cut into small pieces, adds deionized water 1000mL and boils 30 minutes, filters off
Potato ball, complements to 1000mL with deionized water by filtrate；
Described proliferated culture medium is mainly composed of Carnis Bovis seu Bubali cream 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 reducting bacteria/iron-reducing bacterium mixed system
Under anaerobic by reactant liquor A and suspension bacteria liquid B and C with volume ratio as 5:7:8, after being thoroughly mixed, continue old
Changing 40min, obtain the mixed system of sponge iron and sulfate reducting bacteria/iron-reducing bacterium, whole process is passed through nitrogen protection anaerobism
Environment.
(5) after reaction terminates, with deionized deoxygenated water cyclic washing sponge iron/microbe microsphere, at physiological saline solution
Middle immersion, places in refrigerator and preserves at 4 DEG C.
The present embodiment method is used to process containing sulfate and the waste water of heavy metal Cd (II): waste water is formulated as adding Na2SO4
Concentration is 0.5g/L, Cd (NO3)2Concentration is 105mg/L (wherein Cd2+Content is 50mg/L), the sponge iron/sulfate of addition is also
Former bacterium/iron-reducing bacterium mixture concentration is 1g/L, and remaining is water.Reacting under room temperature (25 DEG C), the response time is 24h, every
Sampling every 4h, Cd uses Flame Atomic Absorption Spectrometry Determination concentration.Result is as shown in Figure 1.From figure 1 it appears that along with
Continuing of response time, Cd remaining concentration gradually decreases, and when 24h, its residual concentration only has 7.4mg/L, i.e. can reach 85.2%
Clearance.
Embodiment 3
A kind of sponge iron is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, comprises the following steps:
(1) preparation of sponge iron
At mixed carbon comtent (simple substance carbon dust and the mass ratio of iron cement) 1:2, reaction temperature 1200 DEG C, the bar of response time 25min
Under part, calcine with ferrum mud as a raw material, the sponge iron solid that preparation is conventional.Activating with dilute hydrochloric acid, preparation concentration is the sea of 0.3g/L
Continuous ferrous solution, is designated as reactant liquor A.
(2) preparation of sulfate reducting bacteria SRB
From General Microbiological Culture preservation administrative center of China (Chaoyang District, city of BeiJing, China, postcode 100101, numbering
1.3469) a kind of sulfate reducting bacteria desulfovibrio bought selects 2 rings, is transferred in 30ml nutritional solution, at 35 DEG C
Lucifuge cultivates 3d, and the inoculum concentration with 5% uses proliferated culture medium to be enlarged cultivating 2d, is centrifuged 10min with 3000r/min, obtains
Obtain the exponential phase cell of desulfovibrio, abandon supernatant, make bacteria suspension B, in 4 DEG C of preservations.
Wherein, Nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leaches 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, and 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 leaches cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate
0.5g/L, adjusts pH 7.1, and remaining is water.
(3) preparation of iron-reducing bacterium
Select from General Microbiological Culture preservation administrative center of China (Chaoyang District, city of BeiJing, China, postcode 100101, numbering
1.8048) iron-reduced tuftedmonas 2 ring bought, is transferred in 40ml nutritional solution, cultivates 3d 28 DEG C of lucifuges, with
The inoculum concentration of 5% uses proliferated culture medium to be enlarged cultivating 3d, is centrifuged 10min with 3000r/min, it is thus achieved that iron-reducing bacterium right
Number trophophase cell, abandons supernatant, makes bacteria suspension C, in 4 DEG C of preservations.
Wherein, the Nutrient medium of iron-reducing bacterium is fresh potato juice 900mL, glucose 20g, and remaining is water；Ma Ling
The preparation method of potato juice: remove skin fresh potato 220 grams, be cut into small pieces, adds deionized water 900mL and boils 30 minutes, filters off
Potato ball, complements to 900mL with deionized water by filtrate.
Described proliferated culture medium is mainly composed of Carnis Bovis seu Bubali cream 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 reducting bacteria/iron-reducing bacterium mixed system
Under anaerobic by reactant liquor A and suspension bacteria liquid B and C with volume ratio as 3:7:10, after being thoroughly mixed, continue old
Changing 40min, obtain the mixed system of sponge iron and sulfate reducting bacteria/iron-reducing bacterium, whole process is passed through nitrogen protection anaerobism
Environment.
(5) after reaction terminates, with deionized deoxygenated water cyclic washing sponge iron/microbe microsphere, at physiological saline solution
Middle immersion, places in refrigerator and preserves at 4 DEG C.
The present embodiment method is used to process containing sulfate and the waste water of heavy metal Cd (II): waste water is formulated as adding Na2SO4
Concentration is 0.5g/L, Cd (NO3)2Concentration is 105mg/L (wherein Cd2+Content is 50mg/L), the sponge iron/sulfate of addition is also
Former bacterium/iron-reducing bacterium mixture concentration is 1g/L, and remaining is water.Reacting under room temperature (25 DEG C), the response time is 24h, every
Sampling every 4h, Cd uses Flame Atomic Absorption Spectrometry Determination concentration.Result is as shown in Figure 1.From figure 1 it appears that along with
Continuing of response time, Cd remaining concentration gradually decreases, and when 24h, its residual concentration only has 4.2mg/L, i.e. can reach 91.6%
Clearance.
Embodiment 4
A kind of sponge iron is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, comprises the following steps:
(1) preparation of sponge iron
At mixed carbon comtent (simple substance carbon dust and the mass ratio of iron cement) 1:2, reaction temperature 1200 DEG C, the bar of response time 25min
Under part, calcine with ferrum mud as a raw material, the sponge iron solid that preparation is conventional.Activating with dilute hydrochloric acid, preparation concentration is the sea of 0.7g/L
Continuous ferrous solution, is designated as reactant liquor A.
(2) preparation of sulfate reducting bacteria SRB
From General Microbiological Culture preservation administrative center of China (Chaoyang District, city of BeiJing, China, postcode 100101, numbering
1.3469) a kind of sulfate reducting bacteria desulfovibrio of buying selects 2 rings, it is transferred in 30ml nutritional solution, 35
DEG C lucifuge cultivates 4d, and the inoculum concentration with 5% uses proliferated culture medium to be enlarged cultivating 2d, is centrifuged 10min with 3000r/min,
Obtain the exponential phase cell of desulfovibrio, abandon supernatant, make bacteria suspension B, in 4 DEG C of preservations.
Wherein, Nutrient medium: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·7H2O 0.2g/L, sodium lactate
3.22g/L, yeast leaches 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, and 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 leaches cream 3.5g/L, FeSO4·7H2O 3.0g/L, sodium citrate
0.5g/L, adjusts pH7.3, and remaining is water.
(3) preparation of iron-reducing bacterium
Select from General Microbiological Culture preservation administrative center of China (Chaoyang District, city of BeiJing, China, postcode 100101, numbering
1.8048) iron-reduced tuftedmonas 2 ring bought, is transferred in 40ml nutritional solution, cultivates 5d 28 DEG C of lucifuges, with
The inoculum concentration of 5% uses proliferated culture medium to be enlarged cultivating 2d, is centrifuged 12min with 3000r/min, it is thus achieved that iron-reducing bacterium right
Number trophophase cell, abandons supernatant, makes bacteria suspension C, in 4 DEG C of preservations.
Wherein, the Nutrient medium of iron-reducing bacterium is fresh potato juice 1000mL, glucose 20g, and remaining is water；Ma Ling
The preparation method of potato juice: remove skin fresh potato 220 grams, be cut into small pieces, adds deionized water 1000mL and boils 30 minutes, filters off
Potato ball, complements to 1000mL with deionized water by filtrate；
Described proliferated culture medium is mainly composed of Carnis Bovis seu Bubali cream 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 reducting bacteria/iron-reducing bacterium mixed system
Under anaerobic by reactant liquor A and suspension bacteria liquid B and C with volume ratio as 6:7:7, after being thoroughly mixed, continue old
Changing 40min, obtain the mixed system of sponge iron and sulfate reducting bacteria/iron-reducing bacterium, whole process is passed through nitrogen protection anaerobism
Environment.
(5) after reaction terminates, with deionized deoxygenated water cyclic washing sponge iron/microbe microsphere, at physiological saline solution
Middle immersion, places in refrigerator and preserves at 4 DEG C.
Process containing sulfate and the waste water of heavy metal Cd (II): the preparation of raw material of waste water is for adding Na2SO4Concentration is 0.5g/
L, Cd (NO3)2Concentration is 105mg/L (wherein Cd2+Content is 50mg/L), the sponge iron/sulfate reducting bacteria of addition/ferrum reduction
Bacterium mixture concentration is 1g/L, and remaining is water.Reacting under room temperature (25 DEG C), the response time is 24h, samples at interval of 4h, Cd
Use Flame Atomic Absorption Spectrometry Determination concentration.Result is as it is shown in figure 1, it can be seen that holding along with the response time
Continuous, Cd remaining concentration gradually decreases, and when 24h, its residual concentration only has 6.9mg/L, i.e. can reach the clearance of 86.2%.
In the present invention, SRB Biology-iron Anaerobic Biotechnology combines by the way of sponge iron electronation is strengthened, and makes sulfur
Hydrochlorate reducing bacteria (SRB) is in a kind of active state, and Organic substance is produced electronics by anaerobe digest and decompose, for sulfate also
Former bacterium provides electronics so that sulfate reduction is sulfide by sulfate reducting bacteria.While the generation of sulfide, also with in water
Micro heavy Cd (II) react generation sulfide precipitation, not remove only the Cd (II) of remaining in water, and consume
H2S, prevents it from overflowing from water and entering in air, and the life of staff is produced threat.Visible sponge iron substrate
Add, increase the activity of sulfate reducting bacteria SRB, the maximum sulphur removal potential of SRB can be facilitated out.
The advanced research of common SRB depollution thing technology is based primarily upon the research in terms of electrochemistry, such as Harbin industry
University Zheng Huan sea research anaerobism suspension growth reactor is to sulfate and the removal effect of ammonia nitrogen, within the time of staying of 3d, sulfur
Acid group, ammonia nitrogen removal frank have only reached 69%, 58%, by isolated 31 bacterial strains, find removing sulfate radical and remove ammonia
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 promotes.The Li Guang of Tsing-Hua University congratulates seminar's electric field-enhanced research sulfate reducting bacteria of research and goes to create sulfate process, sends out
Now as I≤1.50mA, along with the increase of electric current, the sulfate reduction rate increases, and optimum current intensity is 1.50mA, averagely also
Former speed is 28.3～35.3mg/d.Compared to these electrochemical researchs, the present invention uses sponge iron SRB anaerobic reduction system not
Only reduce energy consumption, and treatment effeciency, engineering practical operation is simple.
The report processed according to heavy metals Cd (II), under conditions of initial concentration is 50mg/L, action time is
12h, sponge iron can reach 83.26% to the clearance of Cd (II) (Bi Na, the preparation of sphere sponge iron and except cadmium performance study
[J], HBLG08-015).Under conditions of initial concentration is 40mg/L, after effect 7d, Cd (II) is gone by sulfate reducting bacteria
Except rate is up to the 66% (isolation identification of Liu Yan, Dang Zhi, one strain of sulfate reduction bacteria-Desulfovibriosp.strainSRBa-
And remove Cadmium In The Water Body ion research [J]), comparison diagram 1, it can be seen that through sponge iron/sulfate reducting bacteria/iron-reducing bacterium
Microsphere invigoration effect, be 50mg/L at initial concentration, after action time is 1d, to Cd (II) metal in embodiment 1-4
Clearance has respectively reached 90.6%, 85.2%, 91.6% and 86.2%, is above sponge iron and sulfate reducting bacteria is individually made
The removal efficiency of used time, shows that this invention is effectively for the formation of microsphere and the removal of heavy metal Cd (II), at a huge sum of money
Belong to during waste water processes and having a good application prospect.
Embodiments of the present invention are also not restricted to the described embodiments, and other any spirit without departing from the present invention is real
The change made under matter and principle, modify, substitute, combine, simplify, all should be the substitute mode of equivalence, be included in the present invention
Protection domain within.
Claims (10)
1. sponge iron is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, it is characterised in that comprise the following steps:
(1) preparation of sponge iron solution
Being activated by sponge iron solid dilute hydrochloric acid, preparation concentration is the sponge iron solution of 0.3-0.8g/L, is designated as reactant liquor A；
(2) preparation of sulfate reducting bacteria SRB
Transfer to, in desulfovibrio Nutrient medium, keep away at 35-37 DEG C by desulfovibrio (Desulfovibrio) selects 2 rings
Light cultivates 3～5d, uses desulfovibrio proliferated culture medium to be enlarged cultivating 2-3d, centrifugal place with the inoculum concentration of 5-10wt%
Reason, it is thus achieved that the exponential phase cell of desulfovibrio, abandons supernatant, makes bacteria suspension B；
(3) preparation of iron-reducing bacterium
Iron-reduced tuftedmonas (Comamonas) 2 ring is transferred in iron-reducing bacterium Nutrient medium, 28-30 DEG C of lucifuge
Cultivate 3-5d, use iron-reducing bacterium proliferated culture medium to be enlarged cultivating 2-3d, centrifugal treating with the inoculum concentration of 5-10wt%, obtain
Obtain the exponential phase cell of iron-reducing bacterium, abandon supernatant, make bacteria suspension C；
(4) sponge iron and the preparation of sulfate reducting bacteria/iron-reducing bacterium mixture
Under anaerobic, by reactant liquor A, bacteria suspension B and bacteria suspension C, with volume ratio as 1:1:1～1:3:4 mixes, and is aged 40-
60min, after reaction terminates, uses deionized deoxygenated water cyclic washing, soaks in physiological saline solution；Obtain sponge iron and sulphuric acid
The mixture of salt reducing bacteria/iron-reducing bacterium；
(5) sulfate and Cd (II) purify
The mixture of step (4) gained sponge iron with sulfate reducting bacteria/iron-reducing bacterium is mixed with sulfate and Cd (II) waste water
Close, react under room temperature more than 20 hours, purify waste water sulfate and Cd (II) simultaneously.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levying and be, described sponge iron solid is prepared via a method which: with iron cement and simple substance carbon dust as raw material, controls simple substance carbon dust and ferrum
The mass ratio of mud is 1:1-1:3, calcines 20-25min and prepare under the conditions of temperature is 1100-1300 DEG C.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levying and be, the formula of described desulfovibrio Nutrient medium consists of: KH2PO40.6g/L, NH4Cl 1.2g/L, MgSO4·
7H2O 0.2g/L, sodium lactate 3.22g/L, yeast leaches 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, and remaining is water.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levying and be, the formula of described desulfovibrio proliferated culture medium consists of: 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 leaches cream 3.5g/L, FeSO4·7H2O
3.0g/L, sodium citrate 0.5g/L, adjust pH 7.0-7.5, and remaining is water.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levying and be, in step (2), described centrifugal treating is that 3000r/min is centrifuged 10～20min；Bacteria suspension B is in 4 DEG C of preservations；Described de-
Sulfur vibrio (Desulfovibrio) is transferred in 30-40ml desulfovibrio Nutrient medium.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levy and be, described iron-reducing bacterium Nutrient medium: if taking fresh potato juice dry volume, add glucose 20～24g/L, remaining
For water；The preparation method of potato juice: remove skin fresh potato 160～220 grams, be cut into small pieces, add deionized water 800～
1000mL boils 30-35 minute, filters off potato ball, with deionized water, filtrate is complemented to 1000mL.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levying and be, described iron-reducing bacterium proliferated culture medium is mainly composed of Carnis Bovis seu Bubali cream 2.0～2.5g/L, glucose 1.5～2.5g/L, pancreas
Peptone 5.5～6.0g/L, yeast powder 3.0～4.5g/L, pH 6.5～7.5, remaining is water.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levying and be, in step (3), described centrifugal treating is that 3000r/min is centrifuged 10～15min, and bacteria suspension C is in 4 DEG C of preservations；Described ferrum
Reduced tuftedmonas (Comamonas) 2 ring is transferred in 30-40ml iron-reducing bacterium Nutrient medium.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levying and be, the mixture of the described sponge iron soaked in physiological saline solution and sulfate reducting bacteria/iron-reducing bacterium places ice
Case preserves at 4 DEG C.
Sponge iron the most according to claim 1 is collaborative with microorganism goes removing sulfate and the method for Cd (II) waste water, and it is special
Levy and be, step 5) in control sponge iron with sulfate reducting bacteria/iron-reducing bacterium mixture consumption in waste water be 0.5-2g/
L；Described sulfate and Cd (II) waste water contain the Na of 0.5g/L2SO4；Cd (the NO of 105mg/L3)2Concentration is, wherein Cd2+Content
For 50mg/L, remaining is water.
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