CN115851549A - Compound microbial agent, hexavalent chromium removal method and hexavalent chromium wastewater treatment method - Google Patents

Compound microbial agent, hexavalent chromium removal method and hexavalent chromium wastewater treatment method Download PDF

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CN115851549A
CN115851549A CN202211689022.4A CN202211689022A CN115851549A CN 115851549 A CN115851549 A CN 115851549A CN 202211689022 A CN202211689022 A CN 202211689022A CN 115851549 A CN115851549 A CN 115851549A
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hexavalent chromium
microbial agent
compound microbial
agent
parts
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牛永艳
毛婷
王治业
杨涛
叶泽
季彬
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Institute of Biology of Gansu Academy of Sciences
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Institute of Biology of Gansu Academy of Sciences
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Abstract

The invention belongs to the technical field of sewage treatment, and particularly relates to a compound microbial agent, a hexavalent chromium removal method and a hexavalent chromium wastewater treatment method. The compound microbial agent is prepared from the following components in parts by mass: 50 to 60 parts of bacillus cereus, 10 to 20 parts of pseudomonas brassicae and 10 to 20 parts of vitamin corynebacterium. The microbial inoculum provided by the invention can tolerate higher hexavalent chromium concentration, can grow well in the range of pH value of 8-9, has better reduction effect on hexavalent chromium, and has great application prospect in treatment of alkaline hexavalent chromium-containing wastewater and remediation of alkaline hexavalent chromium-polluted soil.

Description

Compound microbial agent, hexavalent chromium removal method and hexavalent chromium wastewater treatment method
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a compound microbial agent, a hexavalent chromium removal method and a hexavalent chromium wastewater treatment method.
Background
The chromium residue is about 2-7% chromium, while the hexavalent chromium, which is a serious environmental pollution, is about 35% of the total chromium content, and the remainder is trivalent chromium. Compared with Cr (III) which is easy to be adsorbed on the soil surface in weak acid and alkaline environments or precipitated in the form of Cr (OH) 3, the Cr (III) has weak mobility.
The traditional chemical repair technology mainly starts from the aspects of chemical reduction and comprehensive treatment, and converts hexavalent chromium into trivalent chromium to achieve the aim of detoxification, but the chemical treatment method inevitably contains a small amount of hexavalent chromium due to the incomplete chemical oxidation-reduction reaction or insufficient added reducing reagent amount (ferrous sulfate, sulfite, alkali metal sulfide or hydrosulfide and the like), so that the human body and the environment are still harmed, and the chemical treatment method increases the total treatment cost of chromium slag due to the large added reducing reagent amount, is easy to generate new secondary pollution in the chemical detoxification process, and is difficult to apply in the actual industrial production.
The microorganisms are various in types, some of the microorganisms can reduce chromium from high-toxicity hexavalent chromium to low-toxicity trivalent chromium, and the microorganisms not only have an adsorption effect on Cr (VI), but also have a catalytic conversion effect on enzyme, a reduction effect, a flocculation effect, a precipitation effect and other more chromium removal ways on metabolites. These findings provide experimental basis for the biological removal of hexavalent chromium, and the new technology for removing hexavalent chromium by a biological method has advantages that other methods cannot compare with, and is environment-friendly, simple in treatment method, easy to control and the like.
Therefore, how to provide a microbial agent for treating hexavalent chromium, which utilizes microorganisms to treat cadmium pollution, is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a composite microbial agent, a hexavalent chromium removing method and a hexavalent chromium wastewater treatment method. The invention provides a reducing microbial inoculum for the transformation of hexavalent chromium. The strain has strong survival ability, complete reduction of hexavalent chromium, short required time, complete microbial degradation and good social, ecological and economic benefits.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a compound microbial agent which is prepared from the following components in parts by mass: 50 to 60 parts of bacillus cereus, 10 to 20 parts of pseudomonas brassicae and 10 to 20 parts of vitamin corynebacterium.
Preferably, the viable count of the bacillus cereus in the composite microbial agent is 1.1 × 10 10 Per ml; the viable count of the pseudomonas brassicae in the compound microbial agent is 3.5 multiplied by 10 19 Per ml; the viable count of the vitamin corynebacterium in the compound microbial agent is 1.4 multiplied by 10 9 One per ml.
The invention also provides a hexavalent chromium removing method, which comprises the following steps: inoculating the compound microbial agent into a culture medium for culture; the culture medium contains hexavalent chromium.
Preferably, the culture medium is Na 2 HPO 4 5~7g/L、KH 2 PO 4 2~4g/L、NaCl 0.3~0.7g/L、NH 4 Cl 0.8~1.2g/L、MgSO 4 .7H 2 O 0.3~0.5g/L、CaCl 2 0.005-0.015 g/L, 3-5 g/L glucose and 1-300 mg/L potassium dichromate.
Preferably, the inoculation volume ratio of the compound microbial agent is 0.5-1.5%.
Preferably, the temperature of the culture is 28-32 ℃; the stirring speed in the culture process is 150-210 r/min.
Preferably, the culture time is 20-50 h; the pH value of the culture is 7-9.
The invention further provides a treatment method of hexavalent chromium wastewater, which comprises the following steps:
(1) Mixing the compound microbial agent with a fixing agent to obtain an immobilized microbial agent;
(2) And (2) mixing the immobilized microbial inoculum obtained in the step (1) with hexavalent chromium-containing wastewater for culture.
Preferably, the fixing agent is polyvinyl alcohol, sodium alginate and activated carbon; the mass ratio of the polyvinyl alcohol to the sodium alginate to the active carbon is (2-3): 3 to 5:1 to 2; the volume ratio of the compound microbial agent to the fixing agent is 1:20.
preferably, the culture time is 30-50 h; aerating for 0.5h every 10-14 h; the addition volume ratio of the immobilized bacteria agent is 8-12%; the content of hexavalent chromium in the hexavalent chromium-containing wastewater is 20-200 mg/l.
Compared with the prior art, the invention has the following beneficial effects:
the microbial agent provided by the invention can be used for treating hexavalent chromium industrial sewage and repairing hexavalent chromium polluted soil. The strain adopted by the invention is separated from natural environment soil, and is obtained by indoor domestication, separation identification and combination. The embodiment proves that the microbial inoculum can tolerate higher hexavalent chromium concentration, can grow well in the range of pH value of 8-9, has better reduction effect on hexavalent chromium, and has great application prospect on treatment of alkaline hexavalent chromium-containing wastewater and remediation of alkaline hexavalent chromium-polluted soil.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows the removal rate of chromium ions at different pH values;
FIG. 2 is a graph of removal rate for different concentrations of chromium ions at different time points;
FIG. 3 shows the removal rate of chromium ions for different fixatives;
FIG. 4 shows control group 5 (experimental group) fixed beads;
FIG. 5 shows the test group 2 (1% charcoal group) fixed pellet;
FIG. 6 shows trivalent chromium obtained by reduction (example 6; experimental group 1).
Detailed Description
The invention provides a compound microbial agent which is prepared from the following components in parts by mass: 50 to 60 parts of bacillus cereus, 10 to 20 parts of pseudomonas brassicae and 10 to 20 parts of vitamin corynebacterium; preferably 52 to 58 parts of bacillus cereus, 12 to 18 parts of pseudomonas brassicae and 12 to 18 parts of vitamin corynebacterium; further preferably 54 to 56 parts of bacillus cereus, 14 to 16 parts of pseudomonas brassicae and 14 to 16 parts of vitamin corynebacterium; more preferably 55 parts of Bacillus cereus, 15 parts of Pseudomonas brassicae and 15 parts of Corynebacterium vitaminum.
In the invention, the viable count of the bacillus cereus in the composite microbial agent is 2.1 multiplied by 10 10 Per ml; the viable count of the pseudomonas brassicae in the compound microbial agent is 8.4 multiplied by 10 9 Per ml; the viable count of the vitamin corynebacterium in the compound microbial agent is 5.31 multiplied by 10 9 Each/ml.
The bacterial strains of the invention comprise: cr-12: bacillus cereus strain MOB-3 Bacillus cereus; cr-14: pseudomonas brassicensis strain Y2 Pseudomonas brassicae; cr-7: corynebacterium vitaerum DSM 20294 Corynebacterium vitamine.
The invention also provides a hexavalent chromium removing method, which comprises the following steps: inoculating the compound microbial agent into a culture medium for culturing; the culture medium contains hexavalent chromium.
In the invention, the culture medium is Na 2 HPO 4 5~7g/L、KH 2 PO 4 2~4g/L、NaCl 0.3~0.7g/L、NH 4 Cl 0.8~1.2g/L、MgSO 4 .7H 2 O 0.3~0.5g/L、CaCl 2 0.005-0.015 g/L, 3-5 g/L glucose and 1-300 mg/L hexavalent chromium concentration; preferably Na 2 HPO 4 6g/L、KH 2 PO 4 3g/L、NaCl 0.4~0.5g/L、NH 4 Cl 0.9~1.1g/L、MgSO 4 .7H 2 O 0.4g/L、CaCl 2 0.007 to 0.013g/L, 4g/L glucose and 20 to 200mg/L hexavalent chromium concentration; further preferred is Na 2 HPO 4 6g/L、KH 2 PO 4 3g/L、NaCl 0.4~0.5g/L、NH 4 Cl 1g/L、MgSO 4 .7H 2 O 0.4g/L、CaCl 2 0.009-0.011 g/L, glucose 4g/L and hexavalent chromium concentration 30-100 mg/L; more preferably Na 2 HPO 4 6.78g/L、KH 2 PO 4 3.0g/L、NaCl 0.5g/L、NH 4 Cl 1.0g/L MgSO 4 .7H 2 O 0.493g/L、CaCl 2 0.011g/L, 4g/L glucose and 50mg/L hexavalent chromium concentration.
In the invention, the inoculation volume ratio of the compound microbial agent is 0.5-1.5%; preferably 0.7 to 1.3 percent; further preferably 0.9 to 1.1%; more preferably 1%.
In the invention, the temperature of the culture is 28-32 ℃; preferably 29 to 31 ℃; further preferably 30 ℃.
In the invention, the stirring speed in the culture process is 150-210 r/min; preferably 160-200 r/min; more preferably 170-190 r/min; more preferably 180r/min.
In the invention, the culture time is 20-50 h; preferably 30-40 h; more preferably 35h.
In the present invention, the pH of the culture is 7 to 9; preferably 8.
The invention further provides a treatment method of hexavalent chromium wastewater, which comprises the following steps:
(1) Mixing the compound microbial agent with a fixing agent to obtain an immobilized microbial agent;
(2) And (2) mixing the immobilized microbial inoculum obtained in the step (1) with hexavalent chromium-containing wastewater for culture.
In the invention, the fixing agent is polyvinyl alcohol, sodium alginate and active carbon; the mass ratio of the polyvinyl alcohol to the sodium alginate to the active carbon is (2-3): 3 to 5:1 to 2; preferably 2.5:4:1.5.
in the invention, the volume ratio of the compound microbial agent to the fixing agent is 1:20.
in the invention, the culture time is 30-50 h; preferably 30-40 h; more preferably 35h.
In the invention, aeration is carried out for 0.5h every 10-14 h; aeration is preferably carried out for 0.5h every 11-13 h; further preferably every 124 h.
In the invention, the addition volume ratio of the immobilized bacteria agent is 8-12%; preferably 9 to 11 percent; more preferably still 10%.
In the invention, the content of hexavalent chromium in the wastewater containing hexavalent chromium is 20-200 mg/l; preferably 30 to 100mg/l; further preferably 50mg/l.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a compound microbial agent comprises the steps of mixing 50 parts of bacillus cereus, 10 parts of pseudomonas brassicae and 10 parts of vitamin corynebacterium; the viable count of the bacillus cereus in the composite microbial agent is 9.8 multiplied by 10 9 Per ml; the viable count of the pseudomonas brassicae in the compound microbial agent is 1.45 multiplied by 10 9 Billions/ml; the live bacteria of the vitamin corynebacterium in the compound microbial agentThe number is 2.36X 10 9 One per ml.
Example 2
A preparation method of a compound microbial agent comprises the steps of mixing 60 parts of bacillus cereus, 20 parts of pseudomonas brassicae and 20 parts of vitamin corynebacterium; the viable count of the bacillus cereus in the composite microbial agent is 4.5 multiplied by 10 10 Per ml; the viable count of the pseudomonas brassicae in the compound microbial agent is 5.6 multiplied by 10 9 Per ml; the viable count of the vitamin corynebacterium in the compound microbial agent is 3.6 multiplied by 10 9 Each/ml.
Example 3
A preparation method of a compound microbial agent comprises the steps of mixing 55 parts of bacillus cereus, 15 parts of pseudomonas brassicae and 15 parts of vitamin corynebacterium; the bacillus cereus is compounded the viable count of the microbial agent is 1.15 × 10 10 Per ml; the viable count of the pseudomonas brassicae in the compound microbial agent is 4.2 multiplied by 10 9 Per ml; the viable count of the vitamin corynebacteria in the compound microbial agent is 1.85 multiplied by 10 9 One per ml.
Example 4
A hexavalent chromium removing method, inoculate the compound microbial inoculum obtained in example 1 according to the volume ratio of 0.5% in a culture medium containing hexavalent chromium, the pH is 7, 28 ℃, the stirring speed is 150r/min and the culture is 20h;
the culture medium is Na 2 HPO 4 5g/L、KH 2 PO 4 2g/L、NaCl 0.3g/L、NH 4 Cl 0.8g/L、MgSO 4 .7H 2 O 0.3g/L、CaCl 2 0.005g/L, 3g/L glucose and 20mg/L hexavalent chromium concentration.
Example 5
A hexavalent chromium removing method, the compound microbial inoculum obtained in the embodiment 2 is inoculated in a culture medium containing hexavalent chromium according to the volume ratio of 1.5 percent, the pH value is 9, the temperature is 32 ℃, and the stirring speed is 200r/min for culturing for 50 hours;
the culture medium is Na 2 HPO 4 7g/L、KH 2 PO 4 4g/L、NaCl 0.7g/L、NH 4 Cl 1.2g/L、MgSO 4 .7H 2 O 0.5g/L、CaCl 2 0.015g/L, 5g/L glucose and 300mg/L hexavalent chromium concentration.
Example 6
A hexavalent chromium removing method, inoculate the compound microbial inoculum obtained in example 3 according to the volume ratio of 1% in the culture medium containing hexavalent chromium, the pH is 8, 30 ℃, the stirring speed is 180r/min and culture 48h;
the culture medium is Na 2 HPO 4 6.78g/L、KH 2 PO 4 3.0g/L、NaCl 0.5g/L、NH 4 Cl 1.0g/LMgSO 4 .7H 2 O 0.493g/L、CaCl 2 0.011g/L, 4g/L glucose and 50mg/L hexavalent chromium concentration.
Example 7
A treatment method of hexavalent chromium wastewater comprises the following steps:
(1) Mixing the compound microbial agent obtained in the embodiment 1 with a fixing agent to obtain an immobilized microbial agent;
(2) Mixing the immobilized microbial agent obtained in the step (1) with waste water containing hexavalent chromium (the content of the hexavalent chromium is 20 mg/l) according to the volume ratio of 8% for culturing for 30 hours, and aerating for 0.5 hour every 10 hours during the culturing period.
The fixing agent is polyvinyl alcohol, sodium alginate and active carbon; the mass ratio is 2:3:1; the volume ratio of the compound microbial agent to the fixing agent is 1:20.
example 8
A treatment method of hexavalent chromium wastewater comprises the following steps:
(1) Mixing the compound microbial agent obtained in the embodiment 2 with a fixing agent to obtain an immobilized microbial agent;
(2) Mixing the immobilized microbial agent obtained in the step (1) with waste water containing hexavalent chromium (the content of the hexavalent chromium is 200 mg/l) according to the volume ratio of 12% for culturing for 50h, and aerating for 0.5h every 14h during the culturing period.
The fixing agent is polyvinyl alcohol, sodium alginate and active carbon; the mass ratio is 3:5:2; the volume ratio of the compound microbial agent to the fixing agent is 1:20.
example 9
A treatment method of hexavalent chromium wastewater comprises the following steps:
(1) Mixing the compound microbial agent obtained in the embodiment 3 with a fixing agent to obtain an immobilized microbial agent;
(2) Mixing the immobilized microbial agent obtained in the step (1) with waste water containing hexavalent chromium (the content of the hexavalent chromium is 50 mg/l) according to the volume ratio of 10% for culturing for 48 hours, and aerating for 0.5 hour every 12 hours during the culturing period.
The fixing agent is polyvinyl alcohol, sodium alginate and active carbon; the mass ratio is 2.5:4:1.5; the volume ratio of the compound microbial agent to the fixing agent is 1:20.
experimental example 1
And (4) a comparison test is carried out to verify the removal capability of the compound microbial agent for hexavalent chromium under different pH values.
Example 6 was set as experimental group 1;
control 1, the other method was the same as in example 6 except that the pH was set to 5 during the culture;
control 2, the other method was the same as in example 6 except that the pH was set to 6 during the culture;
control 3, the other method is the same as example 6 except that pH was set to 7 during the culture;
control 4, the other methods were the same as in example 6 except that the pH was set to 9 during the culture.
After the completion of the incubation, the removal rate of chromium ions was measured for each test group, and the results are shown in table 1 and fig. 1.
TABLE 1
Chromium ion removal Rate%
Experimental group 1 88.75
Control group 1 12.48
Control group 2 26.91
Control group 3 81.58
Control group 4 83.93
As can be seen from the contents in Table 1, the complex microbial inoculant has different capabilities of removing hexavalent chromium under different pH environments, and the optimal removal effect can be achieved only by selecting proper pH.
Experimental example 2
And a comparison test is carried out to verify the removing capability of the compound microbial agent for hexavalent chromium under different concentrations and times of chromium ions. Based on the method of example 6, the concentrations of chromium ions were set to 25, 50, 100, 200, 300mg/l, and the concentrations of chromium ions at different time points were measured, and the results are shown in FIG. 2.
Experimental example 3
And (4) performing a contrast test to verify the removal capacity of the hexavalent chromium of different immobilized bacteria agents.
The method of example 9 was used as experimental group 2 (1% activated carbon group).
Control 5 (experimental group) was prepared in the same manner as in example 9 except that no activated carbon was added to the fixative.
Control 6 (control) was prepared in the same manner as in example 9 except that the complex microorganism microbial agent was not used and only the immobilizing agent was used to culture the wastewater containing hexavalent chromium in a mixed manner.
After the test was completed, the removal rate of chromium ions was measured for each test group, and the results are shown in table 2 and fig. 3.
TABLE 2
Chromium ion removal Rate%
Experimental group 2 95.26
Control group 5 87.27
Control group 6 6.84
As can be seen from the contents shown in table 2, the removal rate of hexavalent chromium can be significantly improved by immobilizing the complex microbial agent, but the selection of the immobilizing agent is particularly important, and the optimal use effect can be achieved only by selecting a proper immobilizing agent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The compound microbial agent is characterized by being prepared from the following components in parts by mass: 50 to 60 parts of bacillus cereus, 10 to 20 parts of pseudomonas brassicae and 10 to 20 parts of vitamin corynebacterium.
2. The compound microbial agent of claim 1Characterized in that the number of viable bacteria in the composite microbial agent is 1.21 multiplied by 10 10 One per ml. The viable count of the bacillus cereus in the composite microbial agent is 1.1 multiplied by 10 10 Per ml; the viable count of the pseudomonas brassicae in the compound microbial agent is 3.5 multiplied by 10 9 Per ml; the viable count of the vitamin corynebacterium in the compound microbial agent is 1.4 multiplied by 10 9 One per ml.
3. A hexavalent chromium removal method is characterized by comprising the following steps: inoculating the compound microbial agent into a culture medium for culturing; the culture medium contains hexavalent chromium.
4. The method of claim 3 wherein said medium is Na 2 HPO 4 5~7g/L、KH 2 PO 4 2~4g/L、NaCl 0.3~0.7g/L、NH 4 Cl 0.8~1.2g/L、MgSO 4 .7H 2 O 0.3~0.5g/L、CaCl 2 0.005-0.015 g/L, 3-5 g/L glucose and 1-300 mg/L potassium dichromate.
5. The method for removing hexavalent chromium according to claim 3, wherein the inoculation volume ratio of the complex microbial inoculant is 0.5-1.5%.
6. The method for removing hexavalent chromium according to claim 3, wherein the temperature of the cultivation is between 28 and 32 ℃; the stirring speed in the culture process is 150-210 r/min.
7. The method for removing hexavalent chromium according to claim 3, wherein the cultivation time is 20 to 50 hours; the pH value of the culture is 7-9.
8. A treatment method of hexavalent chromium wastewater is characterized by comprising the following steps:
(1) Mixing the compound microbial agent with a fixing agent to obtain an immobilized microbial agent;
(2) And (2) mixing the immobilized microbial inoculum obtained in the step (1) with hexavalent chromium-containing wastewater for culture.
9. The method for treating hexavalent chromium wastewater according to claim 8, wherein the fixing agent is polyvinyl alcohol, sodium alginate, and activated carbon; the mass ratio of the polyvinyl alcohol to the sodium alginate to the activated carbon is (2-3): 3 to 5:1 to 2; the volume ratio of the compound microbial agent to the fixing agent is 1:20.
10. the method for treating hexavalent chromium wastewater according to claim 8, wherein the cultivation time is 30 to 50 hours; aerating for 0.5h every 10-14 h; the addition volume ratio of the immobilized bacteria agent is 8-12%; the content of hexavalent chromium in the hexavalent chromium-containing wastewater is 20-200 mg/l.
CN202211689022.4A 2022-12-26 2022-12-26 Compound microbial agent, hexavalent chromium removal method and hexavalent chromium wastewater treatment method Pending CN115851549A (en)

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