CN103613208A - Adsorption plate with high-efficient adsorption and enhanced biodegradation of petroleum hydrocarbon pollutants and preparation method thereof - Google Patents
Adsorption plate with high-efficient adsorption and enhanced biodegradation of petroleum hydrocarbon pollutants and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an adsorption plate with high-efficient adsorption and enhanced biodegradation of petroleum hydrocarbon pollutants and a preparation method thereof. The preparation method comprises the steps of preparing a mixed solution F from NH4HCO3, Ca(NO3)2, (NH4)2HPO4, a urea water solution and an ethylenediaminetetraacetic acid calcium sodium solution; preparing a mixed solution L from urea and a formaldehyde water solution; preparing a mixed solution M from a poly beta-hydroxybutyrate chloroform solution and a polyethylene glycol chloroform solution; dropping the mixed solution L into the mixed solution M to obtain a mixed solution N; dropping the mixed solution F into the mixed solution N to obtain a mixed solution O; spraying distilled water into a container containing liquid nitrogen to prepare ice ball particles, screening and then placing in a mold for compaction; pouring the mixed solution O into the mold for freezing and shaping, then demolding, and freezing to obtain the adsorption plate; culturing the adsorption plate in a petroleum hydrocarbon degrading bacterial culture solution for 24h and then taking out for air-drying. The preparation process disclosed by the invention is simple, and the prepared adsorption plate has high treatment efficiency against petroleum hydrocarbon pollutants and can prevent secondary pollution and destruction to an ecological environment of a water body.
Description
Technical field
The invention belongs to the processing technology field that is subject to petroleum hydrocarbon contaminated water body, particularly adsorption plate and the preparation method of a kind of efficient adsorption and enhanced biodegradation petroleum hydrocarbon contaminant.
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 ecotope 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 biological process.Chemical method is the technological line 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 mechanism, when chemical agent is used in restriction again simultaneously, use biological restoration can show its larger superiority.Physisorphtion is that a kind of processing efficiency 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 sorbent material is remarketed after saturated, if can prepare a kind of biodegradable sorbent material, simultaneously on sorbent material 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 sorbent material 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 microbiological deterioration petroleum hydrocarbon and sorbent material itself, need the participation of nitrogen and phosphorus nutrition element, generally in oil spill water body, the nutritive element such as contained nitrogen and phosphorus cannot meet the needs of microorganism, yet the sorbent material with slow-release nitrogen and 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 slow-release nitrogen and phosphoric and the biological decomposing petroleum hydrocarbon function of physical adsorption one, this has great importance, but also lacks the technology of this aspect at present and study and report for raising water body oil spill processing efficiency, reduction environmental pollution.
Summary of the invention
The adsorption plate and the preparation method that the object of this invention is to provide a kind of efficient adsorption and enhanced biodegradation petroleum hydrocarbon contaminant.
Its concrete steps are as follows:
(1) NH that is 0.35mol/L by 100mL concentration
4hCO
3ca (the NO that solution and 100mL concentration are 0.25mol/L
3)
2solution, obtains mixed liquor A after mixing;
(2) (the NH that is 0.35mol/L by 100mL concentration
4)
2hPO
4solution is slowly added drop-wise in 200mL mixed liquor A under the condition stirring, and obtains mixed liquid B;
(3) in mixed liquid B, dropwise add dense HNO
3to clarification, obtain mixed solution 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 solution C, obtains mixed solution D;
(5) to adding 100mL concentration in mixed solution D, be the aqueous solution of urea of 1.2mol/L, after mixing, obtain mixed solution E;
(6) to adding 50mL concentration in mixed solution E, be the calcio-disodium edetate solution of 0.15mol/L, after mixing, obtain mixed solution F;
(7) aqueous solution of urea that is 45% by 60mL massfraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed solution G; The formalin that is 35% by 10mL massfraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed solution H;
(8) to drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed solution G under 1000r/min agitation condition, making the pH value of solution is 7.2～7.4, obtains mixed liquor I;
(9) mixed solution H is joined in mixed liquor I under 1000r/min agitation condition, be then placed in 43 ℃ of water-baths and stir 90～100 minutes under 1000r/min condition, obtain mixed solution J;
(10) to drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed solution J under 1000r/min agitation condition, the pH value that makes solution is 3.7～3.9, then be placed in 38 ℃ of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed solution K;
(11) 1600mL deionized water is added drop-wise in mixed solution K under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution L;
(12) the polyoxyethylene glycol chloroformic solution that the poly beta-hydroxybutyrate chloroformic solution that is 7.5% by 240mL massfraction and 40mL massfraction are 5.5% fully mixes, and obtains mixed solution M;
(13) 60mL mixed solution L is added drop-wise in mixed solution M under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution N;
(14) 60mL mixed solution F is added drop-wise in mixed solution N under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution O;
(15) distilled water being spurted in the container that liquid nitrogen is housed to quick freezing 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;
(16) garbled ice hockey particle in step (15) is placed in mould cavity and compacting;
(17) mixed solution O is poured in the mould that step (16) obtains, and together puts into liquid nitrogen freeze settled 6 hours, obtain solid mixt after taking out the demoulding; This solid mixt vacuum lyophilization is removed and obtained the slowly adsorption plate of liberating nitrogen and phosphoric after chloroform and ice hockey particle;
(18) adsorption plate step (17) being obtained is cultivated 24h in petroleum hydrocarbon degradation bacteria culture fluid, and petroleum hydrocarbon degradation bacterium is absorbed and fixed on this adsorption 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|;
(19) adsorption plate step (18) being obtained takes out air-dry, can obtain the adsorption plate of efficient adsorption and enhanced biodegradation petroleum hydrocarbon contaminant.
The invention has the beneficial effects as follows, manufacture craft is simple, and the adsorption plate of the efficient adsorption making and enhanced biodegradation petroleum hydrocarbon contaminant is high to petroleum hydrocarbon contaminant processing efficiency, and can not cause secondary pollution and destruction to water ecological setting.
Embodiment
The invention provides adsorption plate and the preparation method of a kind of efficient adsorption and enhanced biodegradation petroleum hydrocarbon contaminant, with an embodiment, the present invention is described below.
Embodiment 1.
The NH that is 0.35mol/L by 100mL concentration
4hCO
3ca (the NO that solution and 100mL concentration are 0.25mol/L
3)
2solution, obtains mixed liquor A after mixing; (the NH that is 0.35mol/L by 100mL concentration
4)
2hPO
4solution is slowly added drop-wise in 200mL mixed liquor A under the condition stirring, and obtains mixed liquid B; In mixed liquid B, dropwise add dense HNO
3to clarification, obtain mixed solution 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 solution C, obtains mixed solution D; To adding 100mL concentration in mixed solution D, be the aqueous solution of urea of 1.2mol/L, after mixing, obtain mixed solution E; To adding 50mL concentration in mixed solution E, be the calcio-disodium edetate solution of 0.15mol/L, after mixing, obtain mixed solution F;
The aqueous solution of urea that is 45% by 60mL massfraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed solution G; The formalin that is 35% by 10mL massfraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed solution H; To drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed solution G under 1000r/min agitation condition, making the pH value of solution is 7.2～7.4, obtains mixed liquor I; Mixed solution H is joined in mixed liquor I under 1000r/min agitation condition, be then placed in 43 ℃ of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed solution J; To drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed solution J under 1000r/min agitation condition, the pH value that makes solution is 3.7～3.9, then be placed in 38 ℃ of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed solution K; 1600mL deionized water is added drop-wise in mixed solution K under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution L;
The polyoxyethylene glycol chloroformic solution that the poly beta-hydroxybutyrate chloroformic solution that is 7.5% by 240mL massfraction and 40mL massfraction are 5.5% fully mixes, and obtains mixed solution M; 60mL mixed solution L is added drop-wise in mixed solution M under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution N;
60mL mixed solution F is added drop-wise in mixed solution N under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution O;
Distilled water being spurted in the container that liquid nitrogen is housed to quick freezing 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 solution O is poured in mould, and together puts into liquid nitrogen freeze settled 6 hours, after the taking-up demoulding, obtain solid mixt; This solid mixt vacuum lyophilization is removed and obtained the slowly adsorption plate of liberating nitrogen and phosphoric after chloroform and ice hockey particle; Adsorption plate is cultivated in petroleum hydrocarbon degradation bacteria culture fluid to 24h taking-up air-dry, can be obtained the adsorption plate of efficient adsorption and enhanced biodegradation petroleum hydrocarbon contaminant.
Be to use efficient adsorption that the inventive method makes and the adsorption plate of enhanced biodegradation petroleum hydrocarbon contaminant to carry out absorption and biodegradation test to the petroleum hydrocarbon in petroleum hydrocarbon contaminated water body below, further illustrate the present invention.
The efficient adsorption that utilization the inventive method makes and the adsorption plate of enhanced biodegradation petroleum hydrocarbon contaminant have carried out absorption and biodegradation test to the petroleum hydrocarbon in petroleum hydrocarbon contaminated water body, result shows that this adsorption plate can effectively adsorb and biological degradation the petroleum hydrocarbon in water body: when the starting point concentration of polluted-water Petroleum Hydrocarbon is 86.4mg/L, in the water body of 500mL, add 12g adsorption plate, after 10 hours, the concentration of water body Petroleum Hydrocarbon is reduced to 0.01mg/L, after 10 days, adsorption plate Petroleum Hydrocarbon concentration does not detect, after 150 days, the quality of adsorption plate reduces by 63%.
Claims (1)
1. adsorption plate and the preparation method of efficient adsorption and enhanced biodegradation petroleum hydrocarbon contaminant, is characterized in that, the concrete steps of this technique are as follows:
(1) NH that is 0.35mol/L by 100mL concentration
4hCO
3ca (the NO that solution and 100mL concentration are 0.25mol/L
3)
2solution, obtains mixed liquor A after mixing;
(2) (the NH that is 0.35mol/L by 100mL concentration
4)
2hPO
4solution is slowly added drop-wise in 200mL mixed liquor A under the condition stirring, and obtains mixed liquid B;
(3) in mixed liquid B, dropwise add dense HNO
3to clarification, obtain mixed solution 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 solution C, obtains mixed solution D;
(5) to adding 100mL concentration in mixed solution D, be the aqueous solution of urea of 1.2mol/L, after mixing, obtain mixed solution E;
(6) to adding 50mL concentration in mixed solution E, be the calcio-disodium edetate solution of 0.15mol/L, after mixing, obtain mixed solution F;
(7) aqueous solution of urea that is 45% by 60mL massfraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed solution G; The formalin that is 35% by 10mL massfraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed solution H;
(8) to drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed solution G under 1000r/min agitation condition, making the pH value of solution is 7.2～7.4, obtains mixed liquor I;
(9) mixed solution H is joined in mixed liquor I under 1000r/min agitation condition, be then placed in 43 ℃ of water-baths and stir 90～100 minutes under 1000r/min condition, obtain mixed solution J;
(10) to drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed solution J under 1000r/min agitation condition, the pH value that makes solution is 3.7～3.9, then be placed in 38 ℃ of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed solution K;
(11) 1600mL deionized water is added drop-wise in mixed solution K under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution L;
(12) the polyoxyethylene glycol chloroformic solution that the poly beta-hydroxybutyrate chloroformic solution that is 7.5% by 240mL massfraction and 40mL massfraction are 5.5% fully mixes, and obtains mixed solution M;
(13) 60mL mixed solution L is added drop-wise in mixed solution M under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution N;
(14) 60mL mixed solution F is added drop-wise in mixed solution N under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution O;
(15) distilled water being spurted in the container that liquid nitrogen is housed to quick freezing 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;
(16) garbled ice hockey particle in step (15) is placed in mould cavity and compacting;
(17) mixed solution O is poured in the mould that step (16) obtains, and together puts into liquid nitrogen freeze settled 6 hours, obtain solid mixt after taking out the demoulding; This solid mixt vacuum lyophilization is removed and obtained the slowly adsorption plate of liberating nitrogen and phosphoric after chloroform and ice hockey particle;
(18) adsorption plate step (17) being obtained is cultivated 24h in petroleum hydrocarbon degradation bacteria culture fluid, and petroleum hydrocarbon degradation bacterium is absorbed and fixed on this adsorption 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;
(19) adsorption plate step (18) being obtained takes out air-dry, can obtain the adsorption plate of efficient adsorption and enhanced biodegradation petroleum hydrocarbon contaminant.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106215901A (en) * | 2016-09-24 | 2016-12-14 | 北京益净环保设备科技有限公司 | For feature board adsorbing quinoline and preparation method thereof |
| CN106215903A (en) * | 2016-09-24 | 2016-12-14 | 北京益净环保设备科技有限公司 | For feature board adsorbing phthalic acid ester and preparation method thereof |
| CN106215902A (en) * | 2016-09-24 | 2016-12-14 | 北京益净环保设备科技有限公司 | Feature board for adsorption of aniline and preparation method thereof |
| CN106238018A (en) * | 2016-09-24 | 2016-12-21 | 北京益净环保设备科技有限公司 | For granule adsorbent adsorbing parathion-methyl and preparation method thereof |
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