CN105800795A - Shell powder degradation agent for degrading petroleum hydrocarbon - Google Patents
Shell powder degradation agent for degrading petroleum hydrocarbon Download PDFInfo
- Publication number
- CN105800795A CN105800795A CN201610203058.5A CN201610203058A CN105800795A CN 105800795 A CN105800795 A CN 105800795A CN 201610203058 A CN201610203058 A CN 201610203058A CN 105800795 A CN105800795 A CN 105800795A
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- China
- Prior art keywords
- conch meal
- degradation agent
- nutritive salt
- shell powder
- salt
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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
-
- 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
- C02F3/347—Use of yeasts or fungi
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mycology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a shell powder degradation agent for degrading petroleum hydrocarbon and carrying nutritive salt. Shell powder serving as a carrier adsorbs nutritive salt capable of being used by microorganisms and containing nitrogen elements and phosphorus elements. The nutritive salt further contains vitamins and microelements. Further, the preferable mole ratio of the nitrogen elements to the phosphorus elements in the nutritive salt is (8:1)-(16:1). The invention further discloses a preparation method of the shell powder degradation agent. The preparation method comprises steps as follows: 1), the nutritive salt is dissolved in water to form a nutritive salt solution and mixed with the shell powder sufficiently; 2), a mixture of the nutritive salt solution and the shell powder is dried. The shell powder degradation agent effectively solves the problem of a poor degradation effect caused by severe loss of nutritive salt in an open water area, has the advantages that the petroleum hydrocarbon degradation efficiency is high, the preparation process is simple and the cost is low, and can be applied to environment restoration in petroleum-polluted water areas such as ports and the like on a large scale.
Description
Technical field
The present invention relates to petroleum hydrocarbon degradation field, particularly relate to the conch meal degradation agent of a kind of carrier band nutritive salt for decomposing petroleum hydrocarbon.
Background technology
Harbour is as the transportation junction passed in and out for safety of ship and berth, ship's navigation, berth, the shop sump oil of discharge in cargo handling process, oil-polluted water, the oils of port district operation land transportation machinery leakage, and Ship's Repair, clean the sump oil and oil-polluted water that produce, harbour is made to become the long-time pollution source of petroleum pollution in ocean, even if under there is no oil tanker accident conditions, oil pollution also can continue to input harbor area, high risks is caused to harbour ecological environment, also the orthobiosis of neighbouring resident is produced significantly impact simultaneously, therefore harbour oil pollution is carried out the effective key repaired and be to control petroleum pollution in ocean.Having physics, the technology such as chemical and biological for the processing method that oil pollution is conventional, wherein bioremediation technology is the first-selected clean environment firendly technology administering harbour water area oil pollution.There is natural petroleum hydrocarbon degradation flora in harbor area environment, but limited by nutritive salt, the petroleum hydrocarbon degradation bacterium in natural environment is difficult to play good degradation effect.Biological renovation method is utilized to remove oil pollution, majority is to promote that by adding trophic factors the measure of growth of microorganism improves oil pollution degradation rate, but owing to harbour is an open environment, affected by the factor such as wave, wind, nutritive salt is easily diluted and runs off, in actual applications, it is difficult to promote microbial degradation petroleum hydrocarbon by adding nitrogen and phosphorus.A kind of solution is by the microbial degradation petroleum hydrocarbon in application vector material adsorption of nitrogen phosphorus recycling environmental stimulation.Carrier material needs possess following characteristics: water insoluble, stability is strong and not degradable, natural material, easily obtain, economical and harbor area environment is not polluted.Research worker has been proposed that many materials possibly as carrier material, and such as peat, clay, vegetable material etc., but the character of these materials is not suitable for being applied in marine environment.Conch meal is a kind of natural biological calcium carbonate material, in the form of sheets or the microstructure of bar form, porosity and specific surface area relatively big, absorbability is splendid, and stability is strong and not degradable, and raw material is easy to get, economical and will not produce to pollute to harbor area.
Summary of the invention
It is an object of the invention to provide the conch meal degradation agent of a kind of carrier band nutritive salt for decomposing petroleum hydrocarbon.
Technical scheme is as follows:
The conch meal degradation agent of described carrier band nutritive salt is with conch meal for carrier, it is adsorbed with and is available for nutritive salt that microorganism utilizes, containing nitrogen element and P elements.In order to advantageously promote the growth of greasy dirt waters Petroleum Hydrocarbon degradation bacteria, improving degradation efficiency, in described nutritive salt, the preferred molar ratio of nitrogen element and P elements is 8:1～16:1, wherein, it is preferable that with carbamide, ammonium salt (such as NH4NO3、(NH4)2SO4、NH4Cl etc.) or nitrate (such as NaNO3、KNO3Deng) as nitrogenous source；Preferred inorganic phosphate, particularly potassium phosphate or sodium ascorbyl phosphate are (such as: NaH2PO4、Na2HPO4、KH2PO4、K2HPO4) as phosphorus source.Further, described nutritive salt can also comprise vitamin and trace element, when nutritive salt is added with vitamin and trace element, it is preferable that soak powder using yeast powder or yeast and originate as vitamin and trace element.At this, skilled person would appreciate that: when needing the nitrogen and phosphorus content ratio accurately controlling in nutritive salt, it should the nutrient source that selection component is relatively single and clear and definite as far as possible, for instance with (NH4)2SO4、NaNO3Deng inorganic nitrogen-containing compound as nitrogenous source, with NaH2PO4、K2HPO4Deng inorganic phosphate as phosphorus source such that it is able to accurately control the N/P ratio in nutritive salt；And when selecting some composition relative complex, containing the Organic substance of the multiple nutrients key element including nitrogen, phosphorus as nutrient source simultaneously (such as peptone, yeast powder, Semen Maydis pulp etc.), N/P ratio is difficulty with accurate control, but still can control in certain proportion.
Specifically, the conch meal degradation agent of described carrier band nutritive salt can be prepared by method acquisition:
(1) nutritive salt is dissolved in water and is configured to nutrient salt solution, then nutrient salt solution and conch meal are sufficiently mixed.In mixed process, conch meal can constantly the nutritive salt in adsorbent solution until reaching adsorption equilibrium.In order to promote the conch meal absorption to solution Middle nutrition salt, stirring or the vibration of certain time can be aided with after the two mixing, for instance: the mixture of the two is shaken 6～10 hours with the rotating speed of 100～200r/min on Kang Shi agitator.In the mixed process of the two, if there being solution constantly to ooze out from mixture, show that the absorption of nutrient salt solution is reached capacity by conch meal, it is not necessary to add nutrient salt solution again；Otherwise, then can consider to continue to add solution.
2) mixture of nutrient salt solution Yu conch meal is dried process, to remove moisture, it is thus achieved that the conch meal degradation agent of carrier band nutritive salt.
For step 1) in the conch meal absorbability to solid nutrient salt, inventor is by repeatedly testing discovery, and the adsorbance of nutritive salt is depended primarily on the particle diameter of conch meal by the conch meal of unit mass.Under normal circumstances, conch meal grain diameter is more little, and its absorbability is more strong；Conch meal for a certain size, under the premise less than its limit adsorbance, nutrient salt solution concentration is more big, conch meal is more big to the adsorbance of wherein nutritive salt, enforcement personnel can regulate nutrient salt solution concentration and conch meal particle diameter according to specific needs voluntarily, thus obtaining the satisfactory conch meal degradation agent of nutritive salt carrying capacity.In the technical program, preferable particle size is sized to the conch meal of 60～100 orders, the conch meal of this size is easily worked acquisition and preparation cost is low, it is also equipped with good absorbability simultaneously, by physics, chemisorbed forms such as skin effect and ionic state absorption, organic or inorganic nutritive salt can be carried out active adsorption.The conch meal specific surface area being recorded 60～100 order particle size range by nitrogen adsorption-BET method is 2.1～3.4m2/g,；It is 3.8～8.5mmol/L that Adsorption thermodynamics and the adsorption kinetic data record its adsorption capacity to ammonium salt, is 1.0～2.4mmol/L to nitrate and phosphatic adsorption capacity.Above-mentioned size is that the conch meal of 60～100 orders can also be adopted and prepares with the following method: the animal flesh within shell is removed clean by (1), then cleans with clear water and dry；(2) with pulverizer shell pulverized and sieve.The shell being wherein used for pulverizing in step (1) can be the shell-fish shells such as Concha Ostreae, scallop, mussel, Conch Meretricis seu Cyclinae or mussel.
In above-mentioned steps 2) in, can first mixture be centrifuged before drying treatment, to remove moisture, thus being greatly shortened the dried time subsequently.
When adding above-mentioned conch meal degradation agent to polluted water region, it is possible to take disposable dosing method, it is also possible to add several times.Wherein, the mode added several times is conducive to the sustained release of nutrient salt in water, makes the nitrogen in water body, phosphorus concentration maintain the level of relative constancy for a long time, thus ensureing the microorganism sustaining degradation to petroleum hydrocarbon.The concrete operations mode added several times is: add conch meal degradation agent to polluted water region, afterwards the nitrogen concentration in periodic detection water body constantly add conch meal degradation agent, makes Water concentration maintain 2～10mg/L all the time, until having degraded.
Compared to the mode directly throwing in nutritive salt, having the beneficial effects that of conch meal degradation agent provided by the invention: effectively overcome the problem causing degradation effect difference because the loss of open water Middle nutrition salt is serious, input mode by conch meal carrier band nutritive salt, dissolubility in water body is oily and tiny oil droplets is easy and conch meal forms polymer by skin effect, these polymer are also the media that in water body, microorganism is very easily adhered to, thus being effectively increased the interface that microorganism contacts with each other with petroleum hydrocarbon and nutritive salt, make petroleum hydrocarbon degradation reaction quickly occurring with conch meal for the microenvironment of carrier and be performed continuously over, thus being greatly enhanced petroleum hydrocarbon degradation efficiency.The advantage that preparation technology is simple, cost is low additionally, conch meal degradation agent provided by the invention also has, can large-scale application in the environment remediation in the oil pollution waters such as harbour.
Detailed description of the invention
Below by way of specific embodiment, technical solution of the present invention and effect are described further.
Embodiment 1
1. the acquisition of conch meal: choose the conch meal that size is 60～100 orders, described conch meal prepares also by following steps: (1) collects the Mollusk shell such as Concha Ostreae, clams, rinse well with clear water again after removing the human body within shell, last 105 DEG C of drying；(2) with pulverizer by shell grinding and sieving.
2. the preparation of the conch meal degradation agent of carrier band nutritive salt:
(1) by 10gNH4NO3And 5gK2HPO4Add in 100mL distilled water, after fully dissolving, obtain nutrient salt solution.Nutrient salt solution is added in the container filling 30g conch meal (particle diameter 60～100 order) and is sufficiently mixed, and the mixture of the two is shaken 6 hours with the rotating speed of 150r/min on Kang Shi agitator, so that the solute in nutrient salt solution is fully adsorbed onto on conch meal.
(2) mixture of conch meal with nutrient salt solution is centrifuged 5～10 minutes to remove moisture under 1000～1500r/min rotating speed, after vacuum lyophilization, namely obtains described conch meal degradation agent.
By the conch meal degradation agent that the present embodiment obtains, the nutritive salt quality of its every gram conch meal carrier band is about 0.12g.
Embodiment 2
(1) by 250g carbamide, 250gNaH2PO4·7H2O and 50g yeast leaching powder is dissolved in 1L water and obtains nutrient salt solution.Nutrient salt solution is added in the container filling 800g conch meal (particle diameter 60～100 order) and is sufficiently mixed, and the mixture of the two is shaken 10 hours with the rotating speed of 150r/min on Kang Shi agitator.
(2) by the mixture centrifugal segregation moisture of conch meal Yu nutrient salt solution, described conch meal degradation agent after vacuum lyophilization, is namely obtained.
By the conch meal degradation agent that the present embodiment obtains, the nutritive salt quality of its every gram conch meal carrier band reaches 0.2g.
The following is the further test to its degradation effect:
Test experiments 1
(1) sea water preprocessing: gather offshore sea waters, Tianjin natural sea-water, laboratory lucifuge stands and preserves 1 week, and absorbent cotton filters；
(2) 3 experimental grouies and 2 matched groups are set, experimental group numbering respectively 1,2,3, matched group numbering respectively 4 and 5, experimental group and matched group are often organized and are arranged some 250mL triangular flasks, each triangular flask all adds 150mL pre-treating seawater and 7.5g No. 0 diesel oil (5%w/v) peculiar to vessel, stands 48h；
(3) in 1,2,3 groups of triangular flasks, the 1g conch meal degradation agent obtained by embodiment 1 is added, with the hospital gauze after 6 layers of sterilizing by above 5 groups of triangular flasks sealing, earthquake incubator is cultivated with 150r/min rotating speed, 37 DEG C of conditions, and the petroleum hydrocarbon content of each group was being measured respectively at the 1st, 2,3,5,10 days, often group measures 3 Duplicate Samples (triangular flask) every time.
Test result indicate that: 1, the petroleum hydrocarbon content in 2,3 groups of sea water quickly reduces, and all reaches 80% at the 3rd day petroleum hydrocarbon degradation rate, and the petroleum hydrocarbon degradation rate of matched group 4 and 5 after 10 days respectively 37% and 40%.
Test experiments 2
(1) arranging 3 experimental grouies and 3 matched groups, often organize and arrange a glass jar (long 27.6cm, wide 28.7cm, high 49.2cm), experimental group is numbered 1～3, and matched group is numbered 4～6.In each glass jar, add pre-treating seawater 20L, be subsequently adding 1kg weathering crude (5%w/v).
(2) mode repeatedly added is taked, the 20g conch meal degradation agent obtained by embodiment 2 is added to 1,2,3 flint glass F cylinders respectively at the 0th, 2,4,6 days, the conch meal of the non-carrier band nutritive salt of equal in quality is added in the same way in 4,5,6 flint glass F cylinders, in different time sections, measure the petroleum hydrocarbon content in each glass jar, and calculate degradation rate.
Test result indicate that: 1, the oil degradation speed of 2, No. 3 experimental grouies is significantly faster than that 4,5, No. 6 matched groups, and each experimental group oil degradation rate in 5 days all reaches 90%, and the oil degradation rate of matched group is the highest after 10 days only reaches 50%.
In above-mentioned test experiments 1 and 2, the degraded of matched group petroleum hydrocarbon is mostly derived from the volatilization of petroleum hydrocarbon；It addition, natural sea-water used in test experiments also exists microorganism, also oil can be produced emulsification.
Claims (10)
1. the conch meal degradation agent for decomposing petroleum hydrocarbon, it is characterised in that: described conch meal degradation agent is with conch meal for carrier, conch meal carrier is adsorbed with and is available for nutritive salt that microorganism utilizes, containing nitrogen element and P elements.
2. conch meal degradation agent according to claim 1, it is characterised in that: in described nutritive salt, the mol ratio of nitrogen element and P elements is 8:1～16:1.
3. conch meal degradation agent according to claim 1 and 2, it is characterised in that: described nutritive salt is using carbamide, ammonium salt or nitrate as nitrogenous source；Using inorganic phosphate as phosphorus source.
4. conch meal degradation agent according to claim 3, it is characterised in that: described ammonium salt is NH4NO3、(NH4)2SO4Or NH4Cl；Described nitrate is NaNO3Or KNO3；Described inorganic phosphate is NaH2PO4、Na2HPO4、KH2PO4Or K2HPO4。
5. conch meal degradation agent according to claim 1 and 2, it is characterised in that: described nutritive salt also comprises vitamin and trace element.
6. conch meal degradation agent according to claim 5, it is characterised in that: described nutritive salt is added with yeast powder or yeast leaching powder.
7. a preparation method for conch meal degradation agent described in claim 1, comprises the following steps: nutritive salt is dissolved in water and is configured to nutrient salt solution by (1), then nutrient salt solution and conch meal is sufficiently mixed；(2) mixture of nutrient salt solution Yu conch meal is dried process.
8. preparation method according to claim 7, it is characterised in that: in described step (1), the size of conch meal is 60～100 orders.
9. the preparation method according to claim 7 or 8, it is characterized in that: in described step (1), after nutrient salt solution and conch meal are sufficiently mixed, the mixture of the two is shaken 6～10 hours with the rotating speed of 100～200r/min on Kang Shi agitator；In described step (2), before drying treatment first by mixture centrifugal segregation moisture.
10. conch meal degradation agent described in claim 1 is applied to the put-on method of polluted water region by one kind, it is characterized in that: add described conch meal degradation agent to polluted water region, nitrogen concentration in periodic detection water body constantly add conch meal degradation agent afterwards, Water concentration is made to maintain 2～10mg/L all the time, until having degraded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610203058.5A CN105800795A (en) | 2016-03-31 | 2016-03-31 | Shell powder degradation agent for degrading petroleum hydrocarbon |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610203058.5A CN105800795A (en) | 2016-03-31 | 2016-03-31 | Shell powder degradation agent for degrading petroleum hydrocarbon |
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| CN201610203058.5A Pending CN105800795A (en) | 2016-03-31 | 2016-03-31 | Shell powder degradation agent for degrading petroleum hydrocarbon |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540302A (en) * | 2019-05-31 | 2019-12-06 | 广东五色时空生态环境科技有限公司 | Pollution source gridding biological intervention pollution-reducing deodorizing process |
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| US3959127A (en) * | 1973-12-05 | 1976-05-25 | The United States Of America As Represented By The Secretary Of The Navy | Biodegradation of oil on water surfaces |
| CN102491529A (en) * | 2011-11-21 | 2012-06-13 | 青岛理工大学 | Method for repairing petroleum pollution mudflat by combining regenerated grease and nutrient |
| JP5155619B2 (en) * | 2007-08-07 | 2013-03-06 | コスモ石油株式会社 | Soil and groundwater purification promoter and purification method |
| CN103523928A (en) * | 2013-07-16 | 2014-01-22 | 中国人民解放军海军医学研究所 | Bacterial agent for bioremediation of oil-polluted water area and preparation method |
-
2016
- 2016-03-31 CN CN201610203058.5A patent/CN105800795A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959127A (en) * | 1973-12-05 | 1976-05-25 | The United States Of America As Represented By The Secretary Of The Navy | Biodegradation of oil on water surfaces |
| JP5155619B2 (en) * | 2007-08-07 | 2013-03-06 | コスモ石油株式会社 | Soil and groundwater purification promoter and purification method |
| CN102491529A (en) * | 2011-11-21 | 2012-06-13 | 青岛理工大学 | Method for repairing petroleum pollution mudflat by combining regenerated grease and nutrient |
| CN103523928A (en) * | 2013-07-16 | 2014-01-22 | 中国人民解放军海军医学研究所 | Bacterial agent for bioremediation of oil-polluted water area and preparation method |
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| KERYN L. SIMONS等: "Carrier mounted bacterial consortium facilitates oil remediation", 《BIORESOURCE TECHNOLOGY》 * |
| PETRA J. SHEPPARD等: "The application of a carrier-based bioremediation strategy for marine oil", 《MARINE POLLUTION BULLETIN》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540302A (en) * | 2019-05-31 | 2019-12-06 | 广东五色时空生态环境科技有限公司 | Pollution source gridding biological intervention pollution-reducing deodorizing process |
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