CN107384973A - A kind of preparation method of support type biology ferro manganese composite oxides - Google Patents
A kind of preparation method of support type biology ferro manganese composite oxides Download PDFInfo
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- CN107384973A CN107384973A CN201710764103.9A CN201710764103A CN107384973A CN 107384973 A CN107384973 A CN 107384973A CN 201710764103 A CN201710764103 A CN 201710764103A CN 107384973 A CN107384973 A CN 107384973A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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Abstract
Invention is related to phenylarsonic acid pollutant and repairs field, and in particular to a kind of preparation method of support type biology ferro manganese composite oxides；It is main to include preparing nutrient broth medium, bacteria group culture, prepare biological ferromanganese culture medium and preparing the steps such as support type biology ferro manganese composite oxides；It, using carbonic acid ore deposit as electron donor, is formed stratiform Biology-iron manganese composite oxide on manganese carbonate surface, that is, support type biology ferro manganese composite oxides is made by pseudomonas putida.The product can be by the phenylarsine acid compounds in soil and secondary product such as arsenite and arsenate, it is fixed on mineral surfaces simultaneously, original position or the showering of phenylarsonic acid pollutant can be achieved, this method is primarily adapted for use in the soil of pollution of surface, this method is simple to operate, processing cost is low, and effect is preferable, non-secondary pollution.
Description
Technical field：
The present invention relates to phenylarsonic acid pollutant to repair field, and in particular to a kind of support type biology ferro manganese composite oxides
Preparation method.
Technical background：
With the sustainable growth of world population and the increasingly raising of Living consumption, the whole world is for grain especially albumen
The demand of matter is increasingly powerful.Pork, egg and chicken obtain the important sources of necessary protein, its sufficient yield as resident
It is to meet the important leverage of broad masses of the people's nutritional need with cheap price.Under traditional aquaculture model, live pig, broiler chicken
General longer with the breeding cycle of laying hen, breeding efficiency is low, aquaculture cost is high, has greatly fettered the yield of the said goods.
Under the forcing of above-mentioned severe situation and under the driving of great market interests, intensive live pig, poultry and egg fowl cultural technique
Using and give birth to, it is intended to reduce aquaculture cost and increase the yield of the said goods while shortening the culture-cycle.To meet above-mentioned want
Ask, promote and using the feed addictive with antibacterial, disease-resistant, rush food conversion and promotion growth with important social value
And economic value.
Phenylarsine acid compounds are the materials containing arsenic acid group on a kind of phenyl ring, are admixed in feed, can substantially be suppressed
Intestinal wall is thickeied the activity of microorganism in animal body, improve the utilization rate and conversion ratio of feed, animal is drawn more support
Point, promote the synthesis of protein and the hematopoiesis function of bone, finally improve the survival rate and Daily gain of poultry.Phenylarsine
The water solubility of acid compounds is high, easily moves in nearby soil and water environment, so as to cause certain journey to quality of water environment
The influence of degree.The phenylarsine acid being discharged into environment, phenylarsine acid compounds can further degrade, be converted into toxicity more
Strong inorganic arsenic, such as arsenite and arsenate.
Ferro manganese composite oxides as a kind of new adsorbent, while have the ferriferous oxide of abundant activated adoption point position with
The strong Mn oxide of surface-active, the improvement and reparation for being applied to pollutant, research find the ferro manganese composite oxides prepared more
Specific surface area is far above ferrihydrite, makes it have the ability of the absorption pentavalent arsenic higher than pure iron Mn oxide or Mn oxide.
Majority of case, the preparation of ferro manganese composite oxides mainly pass through chemical method.Compared with inorganic ferro manganese composite oxides, biology
Ferro manganese composite oxides have higher specific surface area, higher to the adsorption efficiency of pollutant, and preparation cost is cheap, without secondary
Pollution.In soil environment, biological ferro manganese composite oxides are present in mineral surfaces more, and the retention to pollutant is played heavy to closing
The status wanted.Therefore, seek to design a kind of preparation method of support type biology ferro manganese composite oxides for phenylarsine acids chemical combination
The reparation of thing contaminated soil has great significance.
The content of the invention：
The defects of it is an object of the invention to overcome prior art to exist, seek to provide a kind of support type biology ferrimanganic compound
The preparation method of oxide；By aerobic pseudomonas putida (the Pseudomonas putida for choosing divalence iron and manganese oxides
MnB1), culture in the culture medium containing manganese carbonate ore is inoculated into after the bacterium is cultivated and obtains biological ferro manganese composite oxides load
Manganese carbonate ore, be added into the reparation that soil is realized in contaminated soil.
Support type biology ferro manganese composite oxides preparing raw material composition weight of the present invention matches：Pseudomonas putida
Bacterium (Pseudomonas putida MnB1) bacterium solution 1-25 parts, manganese carbonate 0.1-10 parts, beef extract powder 1-5 parts, white peptone 2-10
Part, sodium chloride 1-5 parts, iron ammonium sulfate 0.015-1.5 parts, yeast extract 0.0075-0.75 parts, sodium citrate 0.015-1.5
Part, sodium pyrophosphate 0.005-0.5 parts, deionized water 1000-3000 parts；Wherein manganese carbonate is commercial manganese carbonate.
The preparation method of support type biology ferro manganese composite oxides of the present invention specifically includes following steps：
(1) nutrient broth medium, is prepared
Choose beef extract powder 1-5g, white peptone 2-10g, sodium chloride 1-5g and deionized water 0.5-1.5L and be mixed to get PH=7-
7.4 nutrient broth medium is standby；
(2) bacteria group culture
It is that pseudomonas putida bacterium solution is that 1-5% inoculum concentration is inoculated into prepared by step (1) by volume to choose bacterial strain
In 100-500ml nutrient broth medium, at a temperature of 20-30 DEG C, it is placed in horizontal oscillator tube, setting rotating speed is 100-
200 revs/min of enrichment cultures 1-5 days are standby；
(3) biological ferromanganese culture medium is prepared
Choose iron ammonium sulfate 0.015-1.5g, yeast extract 0.0075-0.75g, sodium citrate 0.015-1.5g, burnt phosphorus
Sour sodium 0.005-0.5g and deionized water 0.5-1.51L are mixed to get the life that pH value is 6.5-7.5 in tool fills in PVC bottle
Thing ferromanganese culture medium is standby；
(4) support type biology ferro manganese composite oxides are prepared
By the obtained bacterial solution of step (2) enrichment, 1-5% inoculum concentration is linked into and prepared containing step (3) by volume
100-500ml biological ferromanganese culture medium tool plug PVC bottle in, then add 0.1-10g manganese carbonate, then will be poly-
Vinyl chloride bottle is placed in turnover oscillator, and it is 20-40 revs/min to set rotating speed, aerobic culture 2- at being 20-30 DEG C in temperature
7d, obtain support type biology ferro manganese composite oxides.
The present invention compared with prior art, its by pseudomonas putida using carbonic acid ore deposit as electron donor, in manganese carbonate table
Face forms stratiform Biology-iron manganese composite oxide, that is, support type biology ferro manganese composite oxides are made；Obtained support type biology
Ferro manganese composite oxides can consolidate the phenylarsine acid compounds in soil and secondary product such as arsenite and arsenate simultaneously
Due to mineral surfaces, the original position or showering, this method that phenylarsonic acid pollutant can be achieved are primarily adapted for use in pollution of surface
Soil, this method is simple to operate, and processing cost is low, and effect is preferable, non-secondary pollution.
Brief description of the drawings：
Fig. 1 is SEM figures before and after the carbonate synthesis manganese load that embodiment 3 is related to, before wherein a is load, after b is load.
Fig. 2：XRD spectra before and after the carbonate synthesis manganese load being related to for embodiment 3, wherein R is manganese carbonate.
Fig. 3：SEM schemes before and after the business manganese carbonate load being related to for embodiment 2, and wherein a is after b is load before load.
Fig. 4：Arsanilic acid contains quantitative change in soil before and after being repaired for the support type biology ferro manganese composite oxides that embodiment 3 is related to
Change.
Embodiment
The invention will be further described by way of example and in conjunction with the accompanying drawings, is not intended to limit the present invention.
Embodiment 1：
The support type biology ferro manganese composite oxides preparing raw material composition weight that the present embodiment is related to matches：Stench is false single
Born of the same parents bacterium (Pseudomonas putida MnB1) bacterium solution 1-25 parts, manganese carbonate 0.1-10 parts, beef extract powder 1-5 parts, white peptone 2-10
Part, sodium chloride 1-5 parts, iron ammonium sulfate 0.015-1.5 parts, yeast extract 0.0075-0.75 parts, sodium citrate 0.015-1.5
Part, sodium pyrophosphate 0.005-0.5 parts, deionized water 1000-3000 parts；Wherein manganese carbonate is commercial manganese carbonate.
The method using support type biology ferro manganese composite oxides rehabilitating soil that the present embodiment is related to specifically include with
Lower step：
(1) nutrient broth medium, is prepared
Choose beef extract powder 1-5g, white peptone 2-10g, sodium chloride 1-5g and deionized water 0.5-1.5L and be mixed to get PH=7-
7.4 nutrient broth medium is standby；
(2) bacteria group culture
Selection bacterial strain is that pseudomonas putida (Pseudomonas putida MnB1) bacterium solution is 1-5%'s by volume
Inoculum concentration is inoculated into the 100-500ml of step (1) preparation nutrient broth medium, at a temperature of 20-30 DEG C, is placed on
In horizontal oscillator tube, it is that 100-200 revs/min of enrichment culture 1-5 days is standby to set rotating speed；
(3) biological ferromanganese culture medium is prepared
Choose iron ammonium sulfate 0.015-1.5g, yeast extract 0.0075-0.75g, sodium citrate 0.015-1.5g, burnt phosphorus
Sour sodium 0.005-0.5g and deionized water 0.5-1.51L are mixed to get the life that pH value is 6.5-7.5 in tool fills in PVC bottle
Thing ferromanganese culture medium is standby；
(4) support type biology ferro manganese composite oxides are prepared
By the obtained bacterial solution of step (2) enrichment, 1-5% inoculum concentration is linked into and prepared containing step (3) by volume
100-500ml biological ferromanganese culture medium tool plug PVC bottle in, then add 0.1-10g manganese carbonate, then will be poly-
Vinyl chloride bottle is placed in turnover oscillator, and it is 20-40 revs/min to set rotating speed, aerobic culture 2- at being 20-30 DEG C in temperature
7d, obtain support type biology ferro manganese composite oxides.
Embodiment 2：
(1) strain source and culture
Selection bacterial strain is pseudomonas putida Pseudomonas putida MnB1, is bought in US mode bacterium is collected
The heart, preserving number ATCC 23483；The bacterium bacterium solution is inoculated into the liquid nutritional meat containing 200ml for 3% inoculum concentration by volume
In soup culture medium, form and be：Beef extract powder 3.0g, peptone 10.0g, sodium chloride 5.0g, deionized water 1L, pH=7.2, in temperature
Spend for 25 DEG C, rotating speed is 150 revs/min of horizontal oscillator tube enrichment culture 3d；
(2) support type biology ferro manganese composite oxides are prepared
By the obtained bacterial solution of step (1) enrichment by volume 5% inoculum concentration be linked into and be containing 200ml culture mediums
Iron ammonium sulfate 0.15g, yeast extract 0.075g, sodium citrate, 0.15g, sodium pyrophosphate, 0.05g, deionized water 1L, pH=
In 6.8 sterile tool plug PVC bottle, while the manganese carbonate for adding 0.8g business (is bought in Chinese medicines group Shanghai chemical agent
Co., Ltd), PVC bottle is placed in turnover oscillator culture, rotating speed is 30 revs/min, is 25 DEG C of aerobic cultures in temperature
2d, support type biology ferro manganese composite oxides can be made.
SEM figures are as shown in Figure 3 before and after the load of business manganese carbonate.It is particle diameter before the load of business manganese carbonate from Fig. 3 (a)
For 0.5-3.0 μm of near-spherical particle.After load (Fig. 3 (b)), there is the biostromal of film-form in business manganese carbonate surface
Ferro manganese composite oxides, the material are the biological ferro manganese composite oxides loaded.
Embodiment 3：
(1) strain source and culture
Selection bacterial strain is pseudomonas putida Pseudomonas putida MnB1, is bought in US mode is collected
The heart, preserving number ATCC 23483.The bacterium bacterium solution is inoculated into the liquid nutritional meat containing 200ml for 2% inoculum concentration by volume
In soup culture medium, form and be：Beef extract powder 3.0g, peptone 10.0g, sodium chloride 5.0g, deionized water 1L, pH=7.2, in temperature
Spend for 25 DEG C, rotating speed is 150 revs/min of horizontal oscillator tube enrichment culture 2d；
(2) support type biology ferro manganese composite oxides are prepared
By the obtained bacterial solution of step (1) enrichment by volume 1% inoculum concentration be linked into and be containing 200ml culture mediums
Iron ammonium sulfate 0.15g, yeast extract 0.075g, sodium citrate, 0.15g, sodium pyrophosphate, 0.05g, deionized water 1L, pH=
In 6.8 sterile tool plug PVC bottle, while the manganese carbonate of 1g synthesis is added, PVC bottle is placed in turnover oscillator training
Support, rotating speed is 30 revs/min, is 25 DEG C of aerobic culture 3d in temperature, obtains support type biology ferro manganese composite oxides.
(3) phenylarsine acid compounds contaminated soil is repaired
The support type biology ferro manganese composite oxides suspension 200ml obtained in step (2) is added into 100g to contain
In 20mg/kg arsanilic acid contaminated soils (particle diameter is about 100 μm), (50 revs/min) 2h is stirred, afterwards at ambient temperature
(25 DEG C), static gas wave refrigerator 7d, the reparation of arsanilic acid contaminated soil can be achieved.As shown in Figure 4, through support type biology ferrimanganic composite oxygen
Compound reparation, the content of arsanilic acid are changed into 2.6mg/kg from 20.0mg/kg, remediation efficiency 87.0%, achieve good repair
Multiple effect.
SEM and XRD spectra be as illustrated in fig. 1 and 2 before and after the load of carbonate synthesis manganese.From Fig. 1 (a), carbonate synthesis manganese is born
It is the near-spherical particle that particle diameter is 1.2-3.1 μm before carrying.After load (Fig. 1 (b)), there is the layer of film-form in manganese carbonate surface
Shape biology ferro manganese composite oxides.(Fig. 2) is understood by XRD results, crystal formation does not find significant change before and after the load of carbonate synthesis manganese,
It is primarily due to the most ferrimanganic complex minerals for unformed or weak crystal formation of biogenic ferro manganese composite oxides.
Claims (2)
1. a kind of preparation method of support type biology ferro manganese composite oxides, it is characterised in that its preparing raw material composition weight matches
For：Pseudomonas putida (Pseudomonas putida MnB1) bacterium solution 1-25 parts, manganese carbonate 0.1-10 parts, beef extract powder 1-5
Part, white peptone 2-10 parts, sodium chloride 1-5 parts, iron ammonium sulfate 0.015-1.5 parts, yeast extract 0.0075-0.75 parts, citric acid
Sodium 0.015-1.5 parts, sodium pyrophosphate 0.005-0.5 parts, deionized water 1000-3000 parts；Wherein manganese carbonate is commercial manganese carbonate.
2. the preparation method of support type biology ferro manganese composite oxides according to claim 1 is characterized in that its specific work
Skill comprises the following steps：
(1) nutrient broth medium, is prepared
Choose beef extract powder 1-5g, white peptone 2-10g, sodium chloride 1-5g and deionized water 0.5-1.5L and be mixed to get PH=7-7.4
Nutrient broth medium it is standby；
(2) bacteria group culture
It is that pseudomonas putida bacterium solution is that 1-5% inoculum concentration is inoculated into the 100- of step (1) preparation by volume to choose bacterial strain
In 500ml nutrient broth medium, at a temperature of 20-30 DEG C, it is placed in horizontal oscillator tube, setting rotating speed is 100-200
Rev/min enrichment culture 1-5 days is standby；
(3) biological ferromanganese culture medium is prepared
Choose iron ammonium sulfate 0.015-1.5g, yeast extract 0.0075-0.75g, sodium citrate 0.015-1.5g, sodium pyrophosphate
0.005-0.5g and deionized water 0.5-1.51L is mixed to get the biological manganese that pH value is 6.5-7.5 in tool fills in PVC bottle
Iron culture medium is standby；
(4) support type biology ferro manganese composite oxides are prepared
The obtained bacterial solution of step (2) enrichment 1-5% by volume inoculum concentration is linked into what is prepared containing step (3)
In the tool plug PVC bottle of 100-500ml biological ferromanganese culture medium, 0.1-10g manganese carbonate is then added, then by polychlorostyrene
Ethene bottle is placed in turnover oscillator, and it is 20-40 revs/min to set rotating speed, aerobic culture 2-7d at being 20-30 DEG C in temperature,
Obtain support type biology ferro manganese composite oxides.
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| CN109277404A (en) * | 2018-11-28 | 2019-01-29 | 青岛理工大学 | A kind of method of bacterium in-situ immobilization As polluted soil |
| CN109277405A (en) * | 2018-11-28 | 2019-01-29 | 青岛理工大学 | A kind of method of nano zero valence iron collaboration bacterial remediation As polluted soil |
| CN109570227A (en) * | 2018-11-28 | 2019-04-05 | 青岛理工大学 | A kind of method of charcoal load nano zero valence iron collaboration bacterial remediation acidification As polluted soil |
| CN109570220A (en) * | 2018-11-28 | 2019-04-05 | 青岛理工大学 | A kind of method that bacteria-induction activity iron and manganese oxides repair As polluted soil under aerobic/micro- aerobic condition |
| CN109759018A (en) * | 2019-03-21 | 2019-05-17 | 湖南农业大学 | The preparation method and application of support type Manganese Ferrite adsorbent |
| CN111234835A (en) * | 2020-02-17 | 2020-06-05 | 兰州大学 | Repairing agent for in-situ repairing heavy metal contaminated soil and in-situ repairing method |
| CN113368811A (en) * | 2021-05-27 | 2021-09-10 | 中南大学 | Biological type iron-manganese composite material, preparation method and application |
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| US11738380B2 (en) | 2018-11-28 | 2023-08-29 | Qingdao university of technology | Method of in-situ remediation of arsenic-contaminated soil |
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| US11738380B2 (en) | 2018-11-28 | 2023-08-29 | Qingdao university of technology | Method of in-situ remediation of arsenic-contaminated soil |
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| CN109570220A (en) * | 2018-11-28 | 2019-04-05 | 青岛理工大学 | A kind of method that bacteria-induction activity iron and manganese oxides repair As polluted soil under aerobic/micro- aerobic condition |
| WO2020108214A1 (en) * | 2018-11-28 | 2020-06-04 | 青岛理工大学 | Method of remediating arsenic pollution in soil using active iron and manganese oxides induced by bacteria under aerobic/microaerobic conditions |
| CN109277404A (en) * | 2018-11-28 | 2019-01-29 | 青岛理工大学 | A kind of method of bacterium in-situ immobilization As polluted soil |
| CN109759018A (en) * | 2019-03-21 | 2019-05-17 | 湖南农业大学 | The preparation method and application of support type Manganese Ferrite adsorbent |
| CN111234835A (en) * | 2020-02-17 | 2020-06-05 | 兰州大学 | Repairing agent for in-situ repairing heavy metal contaminated soil and in-situ repairing method |
| CN111234835B (en) * | 2020-02-17 | 2021-04-30 | 兰州大学 | Repairing agent for in-situ repairing heavy metal contaminated soil and in-situ repairing method |
| CN113368811A (en) * | 2021-05-27 | 2021-09-10 | 中南大学 | Biological type iron-manganese composite material, preparation method and application |
| CN113862307A (en) * | 2021-09-29 | 2021-12-31 | 南京工业大学 | Transition metal doped iron-manganese composite oxide, preparation method and application |
| CN113862307B (en) * | 2021-09-29 | 2024-03-12 | 南京工业大学 | Transition metal doped iron-manganese composite oxide and preparation method and application thereof |
| CN114130405A (en) * | 2021-12-13 | 2022-03-04 | 南京工业大学 | Low-temperature preparation method and application of ozone catalyst of transition metal composite oxide |
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Application publication date: 20171124 |