CN103623785A - Suspended oil absorption plate capable of slowly releasing phosphorus and biologically degrading petroleum hydrocarbon and preparation method thereof - Google Patents
Suspended oil absorption plate capable of slowly releasing phosphorus and biologically degrading petroleum hydrocarbon and preparation method thereof Download PDFInfo
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- CN103623785A CN103623785A CN201310669563.5A CN201310669563A CN103623785A CN 103623785 A CN103623785 A CN 103623785A CN 201310669563 A CN201310669563 A CN 201310669563A CN 103623785 A CN103623785 A CN 103623785A
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Abstract
The invention discloses a suspended oil absorption plate capable of slowly releasing phosphorus and biologically degrading petroleum hydrocarbon and a preparation method thereof. The preparation method comprises the following steps: mixing an NH4HCO3 solution, an NH4H2PO4 solution, a Ca(NO3)2 solution, an NH4OH solution, a hydrochloric acid solution, an NH4Cl water solution and a calcium potassium edentate solution to obtain a mixed solution F; mixing a poly-beta-hydroxybutyrate chloroform solution with a polyethylene glycol chloroform solution to obtain a mixed solution M; dropwise adding the mixed solution F into the mixed solution M to obtain a mixed solution O; spraying distilled water into a container filled with liquid nitrogen to make ice ball granules, sieving, and compacting in a mould; pouring the mixed solution O into the mould, freezing, shaping, demoulding, freezing, culturing in a petroleum hydrocarbon degradation bacteria culture solution for 24 hours, taking out, and performing air-drying to obtain the suspended oil absorption plate capable of slowly releasing phosphorus and biologically degrading petroleum hydrocarbon. The preparation method is simple; the prepared suspended oil absorption plate is high in treatment efficiency of petroleum hydrocarbon pollutants, and does not cause secondary pollution and destruction to a water body ecological environment.
Description
Technical field
The invention belongs to the processing technology field that is subject to petroleum hydrocarbon contaminated water body, particularly a kind of can slowly-releasing phosphorus and suspension oil suction plate and the preparation method of biodegradation petroleum hydrocarbon.
Background technology
In recent years, demand oil and goods thereof day by day being increased along with countries in the world, at sea exploit, load and unload, transport and utilize oil spill accident in oil process to happen occasionally, not only cause a large amount of crude oil to run off, also environment is caused to severe contamination, be on the rise and threatening the ecological environment of water body and land-based area, water body environment, natural resources and culture resources etc. are had to long-term harm, therefore, water body oil spill has become the great environmental problem that people must face.
The method of disposing at present water body oil spill both at home and abroad mainly contains Physical, chemical method and bioanalysis.Chemical method is the technology path of comparative maturity in point-source pollution is administered, and has obtained propagation and employment widely.But in water body oil spill is administered, adopt chemical method, need in water body, add chemical agent, the chemical agent wherein adding may produce secondary pollution on the one hand, can produce short-term or long-term impact to water ecological setting on the other hand.The features such as bioremediation technology has efficiently, economy, safety, non-secondary pollution, become the on-the-spot important selection approach of removing water body oil spill, the oil sheet that particularly cannot remove mechanical device, when chemical agent is used in restriction again simultaneously, use biological prosthetic its larger superiority of showing.Physisorphtion is that a kind for the treatment of effeciency is high, cost is low, without sediment pollution, simple to operate and can not cause to water ecological setting the method for secondary pollution and destruction, can solve preferably the existing problem of chemical method.But, the cycle of bioremediation technology is long, physisorphtion faces absorption needs the problem that adsorbent is remarketed after saturated, if can prepare a kind of biodegradable adsorbent, simultaneously on adsorbent fixedly petroleum hydrocarbon degradation bacterium to improve the clearance of petroleum hydrocarbon, effect by microbe inoculation after absorption is saturated is adsorbent petroleum hydrocarbon degradation, and final biodegradable adsorbent itself also can thoroughly degrade, and can address this problem.Physisorphtion and fixation of microbe are carried out to enhancing degradation and combine, for disposing water body oil spill, will there is larger advantage.
In the process of microbial degradation petroleum hydrocarbon and adsorbent itself, need the participation of phosphorus nutrition element, generally in oil spill water body, the contained nutrients such as phosphorus cannot meet the needs of microorganism, yet the adsorbent with slowly-releasing phosphorus function can meet this requirement.For physisorphtion and fixation of microbe being carried out to the technology that enhancing degradation combines, in processing, water body oil spill obtains further propagation and employment, need to develop the material simultaneously with slowly-releasing P elements and physical absorption-biodegradation petroleum hydrocarbon function, this has great importance, but also lacks the technology of this aspect at present and study and report for raising water body oil spill treatment effeciency, reduction environmental pollution.
Summary of the invention
The object of this invention is to provide a kind of can slowly-releasing phosphorus and suspension oil suction plate and the preparation method of biodegradation petroleum hydrocarbon.Its concrete steps are as follows:
(1) NH that is 0.35mol/L by 100mL concentration
4hCO
3the NH that solution and 100mL concentration are 0.62mol/L
4h
2pO
4mix, obtain mixed liquor A l, the NH that is then 0.01mol/L by concentration
4oH solution and concentration are that the pH value of the hydrochloric acid solution adjusting mixed liquor A l of 0.01mol/L is 9.0, obtain mixed liquor A;
(2) 200mL mixed liquor A is slowly added drop-wise under stirring condition to the Ca (NO that 300mL concentration is 0.025mol/L
3)
2in solution, obtain mixed liquid B;
(3) in mixed liquid B, dropwise add dense HNO
3to clarification, obtain mixed liquor C;
(4) it is 3.5 that the salpeter solution that the NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/L regulates the pH value of mixed liquor C, obtains mixed liquor D;
(5) to adding 100mL concentration in mixed liquor D, be the aqueous solution of urea of 1.2mol/L, after mixing, obtain mixed liquor E;
(6) to adding 50mL concentration in mixed liquor E, be the calcio-disodium edetate solution of 0.15mol/L, after mixing, obtain mixed liquor F;
(7) the polyethylene glycol chloroformic solution that the poly beta-hydroxybutyrate chloroformic solution that is 7.5% by 240mL mass fraction and 40mL mass fraction are 5.5% fully mixes, and obtains mixed liquor M;
(8) 60mL mixed liquor F is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
(9) distilled water being spurted in the container that liquid nitrogen is housed to snap frozen and made ice hockey particle, is that the ice hockey particle of 50~100 μ m is stand-by with choosing grain size scope after screen cloth screening;
(10) garbled ice hockey particle in step (9) is placed in mould cavity and compacting;
(11) mixed liquor O is poured in the mould that step (10) obtains, and together puts into liquid nitrogen freeze settled 6 hours, obtain solid mixt after taking out the demoulding; The suspension oil suction plate of P elements will be obtained slowly discharging after this solid mixt vacuum freeze drying removal chloroform and ice hockey particle;
(12) suspension oil suction plate step (11) being obtained is cultivated 24h in petroleum hydrocarbon degradation bacteria culture fluid, and petroleum hydrocarbon degradation bacterium is absorbed and fixed on this suspension oil suction plate, and wherein the bacteria containing amount of petroleum hydrocarbon degradation bacteria culture fluid is 5 * 10
10cFU/ml, the consisting of of nutrient solution: NH
4nO
3: 2.0gL
-1, NaCl:10.5gL
-1, KH
2pO
4: 2.5gL
-1, FeCl
3: 0.10gL
-1, MgSO
4: 3.5gL
-1, CaCl
22H
2o:0.15gL
-1;
(13) the suspension oil suction plate that step (12) obtained takes out air-dry, and can obtain can slowly-releasing phosphorus and the suspension oil suction plate of biodegradation petroleum hydrocarbon.
The invention has the beneficial effects as follows, manufacture craft is simple, make can slowly-releasing phosphorus and the suspension oil suction plate of biodegradation petroleum hydrocarbon high to petroleum hydrocarbon contaminant treatment effeciency, and can not cause secondary pollution and destruction to water ecological setting.
The specific embodiment
The invention provides a kind of can slowly-releasing phosphorus and suspension oil suction plate and the preparation method of biodegradation petroleum hydrocarbon, with an embodiment, the present invention is described below.
Embodiment 1.
The NH that is 0.35mol/L by 100mL concentration
4hCO
3the NH that solution and 100mL concentration are 0.62mol/L
4h
2pO
4mix, obtain mixed liquor A l, the NH that is then 0.01mol/L by concentration
4oH solution and concentration are that the pH value of the hydrochloric acid solution adjusting mixed liquor A l of 0.01mol/L is 9.0, obtain mixed liquor A; 200mL mixed liquor A is slowly added drop-wise under stirring condition to the Ca (NO that 300mL concentration is 0.025mol/L
3)
2in solution, obtain mixed liquid B; In mixed liquid B, dropwise add dense HNO
3to clarification, obtain mixed liquor C; It is 3.5 that the salpeter solution that the NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/L regulates the pH value of mixed liquor C, obtains mixed liquor D; To adding 100mL concentration in mixed liquor D, be the aqueous solution of urea of 1.2mol/L, after mixing, obtain mixed liquor E; To adding 50mL concentration in mixed liquor E, be the calcio-disodium edetate solution of 0.15mol/L, after mixing, obtain mixed liquor F;
The polyethylene glycol chloroformic solution that the poly beta-hydroxybutyrate chloroformic solution that is 7.5% by 240mL mass fraction and 40mL mass fraction are 5.5% fully mixes, and obtains mixed liquor M;
60mL mixed liquor F is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
Distilled water being spurted in the container that liquid nitrogen is housed to snap frozen and made ice hockey particle, is that the ice hockey particle of 50~100 μ m is placed in mould cavity and compacting with choosing grain size scope after screen cloth screening; Mixed liquor O is poured in mould, and together puts into liquid nitrogen freeze settled 6 hours, after the taking-up demoulding, obtain solid mixt; The suspension oil suction plate of P elements will be obtained slowly discharging after this solid mixt vacuum freeze drying removal chloroform and ice hockey particle; Suspension oil suction plate is cultivated to 24h in petroleum hydrocarbon degradation bacteria culture fluid and take out air-dryly, can obtain can slowly-releasing phosphorus and the suspension oil suction plate of biodegradation petroleum hydrocarbon.
Be below use that the inventive method makes can slowly-releasing phosphorus and the suspension oil suction plate of biodegradation petroleum hydrocarbon the petroleum hydrocarbon in petroleum hydrocarbon contaminated water body has been carried out to absorption and biodegradation test, further illustrate the present invention.
Use that the inventive method makes can slowly-releasing phosphorus and the suspension oil suction plate of biodegradation petroleum hydrocarbon the petroleum hydrocarbon in petroleum hydrocarbon contaminated water body has been carried out to absorption and biodegradation test, result shows that this suspension oil suction plate can effectively adsorb and biodegradation the petroleum hydrocarbon in water body: when the initial concentration of polluted-water Petroleum Hydrocarbon is 86.4mg/L, in the water body of 500mL, add 12g oil suction plate, after 10 hours, the concentration of water body Petroleum Hydrocarbon is reduced to 0.01mg/L, 10 days afterwards suspension oil suction plate Petroleum Hydrocarbon concentration do not detect, the quality reduction by 42% of suspension oil suction plate afterwards in 150 days.
Claims (1)
1. can slowly-releasing phosphorus and suspension oil suction plate and the preparation method of biodegradation petroleum hydrocarbon, it is characterized in that, the concrete steps of the method are as follows:
(1) NH that is 0.35mol/L by 100mL concentration
4hCO
3the NH that solution and 100mL concentration are 0.62mol/L
4h
2pO
4mix, obtain mixed liquor A l, the NH that is then 0.01mol/L by concentration
4oH solution and concentration are that the pH value of the hydrochloric acid solution adjusting mixed liquor A l of 0.01mol/L is 9.0, obtain mixed liquor A;
(2) 200mL mixed liquor A is slowly added drop-wise under stirring condition to the Ca (NO that 300mL concentration is 0.025mol/L
3)
2in solution, obtain mixed liquid B;
(3) in mixed liquid B, dropwise add dense HNO
3to clarification. obtain mixed liquor C;
(4) it is 3.5 that the salpeter solution that the NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/L regulates the pH value of mixed liquor C, obtains mixed liquor D;
(5) to adding 100mL concentration in mixed liquor D, be the aqueous solution of urea of 1.2mol/L, after mixing, obtain mixed liquor E;
(6) to adding 50mL concentration in mixed liquor E, be the calcio-disodium edetate solution of 0.15mol/L, after mixing, obtain mixed liquor F;
(7) the polyethylene glycol chloroformic solution that the poly beta-hydroxybutyrate chloroformic solution that is 7.5% by 240mL mass fraction and 40mL mass fraction are 5.5% fully mixes, and obtains mixed liquor M;
(8) 60mL mixed liquor F is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
(9) distilled water being spurted in the container that liquid nitrogen is housed to snap frozen and made ice hockey particle, is that the ice hockey particle of 50~100 μ m is stand-by with choosing grain size scope after screen cloth screening;
(10) garbled ice hockey particle in step (9) is placed in mould cavity and compacting;
(11) mixed liquor O is poured in the mould that step (10) obtains, and together puts into liquid nitrogen freeze settled 6 hours, obtain solid mixt after taking out the demoulding; The suspension oil suction plate of P elements will be obtained slowly discharging after this solid mixt vacuum freeze drying removal chloroform and ice hockey particle;
(12) suspension oil suction plate step (11) being obtained is cultivated 24h in petroleum hydrocarbon degradation bacteria culture fluid, and petroleum hydrocarbon degradation bacterium is absorbed and fixed on this suspension oil suction plate, and wherein the bacteria containing amount of petroleum hydrocarbon degradation bacteria culture fluid is 5 * 10
10cFU/ml, the consisting of of nutrient solution: NH
4nO
3: 2.0gL
-1, NaCl:10.5gL
-1, KH
2pO
4: 2.5gL
-1, FeCl
3: 0.10gL
-1, MgSO
4: 3.5gL
-1, CaCl
22H
2o:0.15gL
-1:
(13) the suspension oil suction plate that step (12) obtained takes out air-dry, and can obtain can slowly-releasing phosphorus and the suspension oil suction plate of biodegradation petroleum hydrocarbon.
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Citations (5)
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WO2004058647A1 (en) * | 2002-12-31 | 2004-07-15 | Ku-Su Kim | Wastewater disposal agent and process for preparing thereof |
CN102500340A (en) * | 2011-09-30 | 2012-06-20 | 北京师范大学 | Porous particle with functions of adsorbing and biodegrading petroleum hydrocarbon and preparation method of porous particle |
CN102963959A (en) * | 2012-12-03 | 2013-03-13 | 北京师范大学 | Preparation method of microsphere particles capable of slowly releasing nitrogen and adsorbing-biologically degrading petroleum hydrocarbon |
CN102976499A (en) * | 2012-12-03 | 2013-03-20 | 北京师范大学 | Method for preparing composite board capable of simultaneously slowly releasing nitrogen and adsorbing/biologically degrading petroleum hydrocarbons |
WO2013102729A1 (en) * | 2012-01-03 | 2013-07-11 | Compagnie Financiere Et De Participations Roullier | Phosphate-based granular material, process for manufacturing same and use thereof in a device for removing phosphates from wastewaters |
-
2013
- 2013-12-12 CN CN201310669563.5A patent/CN103623785B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004058647A1 (en) * | 2002-12-31 | 2004-07-15 | Ku-Su Kim | Wastewater disposal agent and process for preparing thereof |
CN102500340A (en) * | 2011-09-30 | 2012-06-20 | 北京师范大学 | Porous particle with functions of adsorbing and biodegrading petroleum hydrocarbon and preparation method of porous particle |
WO2013102729A1 (en) * | 2012-01-03 | 2013-07-11 | Compagnie Financiere Et De Participations Roullier | Phosphate-based granular material, process for manufacturing same and use thereof in a device for removing phosphates from wastewaters |
CN102963959A (en) * | 2012-12-03 | 2013-03-13 | 北京师范大学 | Preparation method of microsphere particles capable of slowly releasing nitrogen and adsorbing-biologically degrading petroleum hydrocarbon |
CN102976499A (en) * | 2012-12-03 | 2013-03-20 | 北京师范大学 | Method for preparing composite board capable of simultaneously slowly releasing nitrogen and adsorbing/biologically degrading petroleum hydrocarbons |
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Granted publication date: 20150909 Termination date: 20161212 |