CN105481215B - A kind of method using microorganism recycling oil-containing hazardous waste Crude Oil - Google Patents

A kind of method using microorganism recycling oil-containing hazardous waste Crude Oil Download PDF

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CN105481215B
CN105481215B CN201510664969.3A CN201510664969A CN105481215B CN 105481215 B CN105481215 B CN 105481215B CN 201510664969 A CN201510664969 A CN 201510664969A CN 105481215 B CN105481215 B CN 105481215B
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oil
crude oil
dangerous waste
recycling
flora
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CN105481215A (en
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辛宝平
蔡金慧
杨依然
王佳
祁诗月
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Beijing Institute of Technology BIT
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/20Sludge processing

Abstract

The present invention relates to it is a kind of using high-effective microorganism by the method for landing oil soil/greasy filth/bed mud recycling treatment, belong to reclamation of solid wastes processing technology field.Landing oil soil/greasy filth/bed mud from oil recovery and oil refining industry is put by certain solid-to-liquid ratio in hardly biodegradableorganic after sieving removes fragment with mineral nutrition liquid, access high effective microbial community, after running 39 days, crude oil, which separates with substrate and acts on float downward to liquid level in aeration, realizes recycling, crude oil recovery rate 60 90%, the mass ratio of dangerous waste crude oil residual quantity is 0.5 3.0%.The present invention by oil-containing dangerous waste Crude Oil separation and Extraction, is greatly reduced oily soil/greasy filth/bed mud Central Plains oil content using microorganism Compound bacterium, and this method is easy to operate, environmentally protective, of low cost, resource reclaim, has higher environmental benefit and economic benefit.

Description

A kind of method using microorganism recycling oil-containing hazardous waste Crude Oil
Technical field
The present invention relates to a kind of sides using oil-containings hazardous waste Crude Oils such as microorganism oil recovery soil, greasy filth and bed muds Method belongs to reclamation of solid wastes processing technology field.
Background technology
A large amount of oily solid sludges are generated in oil exploitation, collection, transport and storage process, crude content is usually 10% Left and right even more high.These oily solid sludges not only have the combustibility of height, and due to benzene class, phenols and anthracene class substance Presence also show certain bio-toxicity, to surrounding body, soil and environment structure endanger.This kind of oily solid sludge quilt China is classified as hazardous waste, collects, transports, storage and disposal are strictly supervised.Oil-containing dangerous waste mainly include landing oil soil, Exploit greasy filth and storage tank bed mud etc..Often exploit about 200,000 tons of the oil-containing solid waste that ten million ton of crude oil generates.It produces oil per year and surpasses in China Hundred million tons, micro- useless 3,000,000 tons of amount incomplete statistics of oil-containing or more.
By regulation, hazardous waste must be carried out harmless treatment by qualified unit, and dangerous waste manufacturing enterprise needs to pay Receive corresponding disposal expense.But due to history, the processing of China's oil-containing dangerous waste still continue to use mostly early stage simple landfill or The method filled after curing, there are serious security risk and environmental hazards, do not realize innoxious purpose.High temperature incineration Although technique disclosure satisfy that the harmless treatment of oil-containing dangerous waste, but excessively high disposal expense brings huge warp to dangerous waste manufacturing enterprise Ji burden, while cause the serious waste of crude resources and the complete destruction of matrix soil.Therefore, no matter from environmental protection or From the perspective of energy recovery, the recycling treatment for recycling crude oil to greatest extent represents the development side of oil-containing dangerous waste disposal technology To.
Crude oil and soil are separated using organic solvent and then completes the recycling of crude oil, are current oil-containing dangerous waste recycling treatments Main technique.Although the technique can realize the efficient and quick recycling of crude oil, a large amount of uses of organic solvent cause be System danger significantly improves, and operating condition is also quite harsh;And the regeneration of organic solvent needs high temperature distillation, energy consumption Greatly, it is of high cost, process is complicated.Green, safety, economy, efficient oil-containing dangerous waste resource processing new technology are urgently researched and developed.
Microbial technique is introduced the recycling treatment of oil-containing dangerous waste by the present invention, is realized under the temperate condition of normal temperature and pressure The recycling of oil-containing dangerous waste Crude Oil.Its principle is:Special efficacy microorganism species are using crude oil as carbon source and energy decomposition long-chain molecule And synthetic surfactant.Long-chain molecule shortens the cohesive force reduced between crude oil and soil, the generation of surfactant into One step promotes the separation between crude oil and soil.By the native Central Plains oil content of crude oil recovery oil by 5.0-20% or so drops To 1.0%-4.0%, the crude oil recovery rate of 70-90% is realized, to meet 0.3% agricultural or 0.5% work standard depth Processing is laid a good foundation.
The content of the invention
The invention aims to landing oil soil, the exploitation oil-containings such as greasy filth and storage tank bed mud dangerous waste are carried out at recycling Reason proposes a kind of microbial process of the recycling crude oil based on hardly biodegradableorganic.The purpose of the present invention is pass through following skills What art scheme was realized.
The present invention recycles method of the crude oil so as to fulfill oil-containing dangerous waste recycling treatment, tool to be a kind of using microbial technique Body step is as follows:
Step 1, the culture of high efficiency flora
High effective microbial community for crude oil recovery be from the oil-polluted soils and bed mud of various regions selection and breeding compounding and Come;Including 45% Alkanindiges sp., 30% Acinetobacter sp., 15% Pseudomonas sp., The Arthrobacter sp. of 5% Cupriavidus sp. and 5%;With oil-containing Solution culture method high efficiency flora, nutrient solution is matched somebody with somebody Side:NH4NO3Or KNO3Or NH4CI or (NH4)2SO4, 0.4~2.0g/L;Na2HPO4Or KH2PO4, 0.4~2.0g/L;NaCl, 0.2~1.0g/L;MgSO4, 0.2~1.0g/L;CaCl2, 0.01~0.05g/L;FeSO4, 0.01~0.05g/L;Crude oil, 10 ~50g/L;pH 6.0-8.0;Uniformly divided by being ultrasonically treated or adding in a certain amount of Tweens surfactant crude oil and formed Scattered emulsion;Nutrient solution is prepared with distilled water or tap water;Flora is cultivated in shaking table or aeration and biological fermentation tank, condition is such as Under:40-200 revs/min of temperature 20-40 degree, shaking table or speed of agitator, 0.1-0.5 times of nutrient solution volume/minute of aeration quantity;Training After bringing about 2-4 days up, cell growth reaches stationary phase, cell turbidity 300-1200FTU;High efficiency flora suspension is used in oil-containing dangerous waste The microorganism separation and recycling of crude oil;
Stone, wooden unit, cloth, plastics and straw are removed Step 2: crushing and sieving oily soil, greasy filth, bed mud oil-containing dangerous waste Stalk class sundries, stores for future use;
Step 3: the microorganism separation and recycling of oil-containing dangerous waste Crude Oil
Mineral nutrition liquid is prepared, formula is as follows:NH4NO3Or KNO3Or NH4CI or (NH4)2SO4, 0.1~1.0g/L; Na2HPO4Or KH2PO4, 0.1~1.0g/L;NaCl, 0.1~0.5g/L;MgSO4, 0.1~0.5g/L;CaCl2, 0.01~ 0.05g/L;FeSO4, 0.01~0.05g/L;pH 6.0-8.0;Micro- life of oil-containing dangerous waste Crude Oil is realized in mud reactor Object separates and recycling;Mud system is formulated by a certain percentage by oil-containing dangerous waste and mineral nutrition liquid, mineral nutrition liquid: The volume ratio of oil-containing dangerous waste is 3:1-6:1, high efficiency flora inoculum concentration be 2%-10%, reaction temperature be 20-40 degree, aeration quantity For 0.05-0.5 times of nutrient solution volume/minute, speed of agitator is 40-200 revs/min;After operation 3-9 days, oil-containing dangerous waste Central Plains Oil is separated with substrate and in aeration effect float downward to reactor liquid level, crude oil recovery rate 60-90%, and the quality of dangerous waste crude oil is residual Allowance is 0.5-3.0%;Operational process regards flora growth situation and suitably supplements the volume ratio of microbial inoculum as 2%-10%.Slurry reaction Body accumulates 1-500 cubes, tool heating, aeration and agitating device (see Fig. 1).
The present invention uses the advantageous effect of above technical scheme
The microbial resources treatment technology of crude oil is recycled from oil-containing dangerous waste the present invention is based on mud reactor, compared with heat Solution and solidification method undoubtedly have resource reclaim advantage and good economic benefit, compared with organic solvent washing recycling rule performance Go out the characteristics of green, environmentally friendly, safe and economic.
Description of the drawings
It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is attached drawing needed in technology description to be briefly described.
Fig. 1 is the bioreactor of the present invention and the structure diagram of mud reactor.
1 is motor in figure, and 2 be exhaust outlet, and 3 be circulating water outlet, and 4 be pH, Do probe, and 5 be aerator, and 6 be discharging Mouthful, 7 be feeding port, and 8 be blender, and 9 be heating water bath water inlet
Specific embodiment
With reference to examples of implementation, the present invention is described in detail.
Embodiment 1
1. the culture of high efficiency flora
High efficiency flora includes Alkanindiges sp., Acinetobacter sp., Pseudomonas sp., Cupriavidus sp. and Arthrobacter sp..Nutrient solution prescription:NH4NO3,1.0g/L;Na2HPO4,1.0g/L; NaCl,0.5g/L;MgSO4,0.5g/L;CaCl2,0.05g/L;FeSO4,0.01g/L;Crude oil, 20g/L;pH 7.2.It adds in 1.0% (v/v) polysorbas20 is sufficiently stirred so that crude oil forms emulsion and evenly spreads in culture solution.It is prepared and sought with tap water Nutrient solution.Flora is cultivated in 10 liters of biological fermentation tanks, condition is as follows:35 degree of temperature, 80 revs/min of speed of agitator, aeration quantity 2 Liter/min.After culture 4 days, cell turbidity reaches 600FTU, and high efficiency flora seed liquor is spare.
2. oily soil is crushed and spare after the sundries such as removing stone, wooden unit, cloth, plastics and stalk that sieve;
3. the microorganism separation and recycling of oily soil Crude Oil
Mineral nutrition liquid is prepared, formula is as follows:KNO3,0.5g/L;KH2PO4,0.5g/L;NaCl,0.25g/L; MgSO4,0.25g/L;CaCl2,0.01g/L;FeSO4,0.01g/L;pH 7.0.Crude oil is realized in 100 liters of mud reactors Microorganism separates and recycling.Mud system is formulated by oily soil and mineral nutrition liquid, mineral nutrition liquid:Oily soil ratio is 4:1 (V/V), high efficiency flora inoculum concentration 10% for the first time, 35 degree of reaction temperature, 20 liters/min of aeration quantity, 120 revs/min of speed of agitator Clock.During operation, the crude oil for once floating on liquid level is collected, and adds high efficiency flora 5% (v/v) within every two days.After operation 5 days, Crude oil adds up the rate of recovery 80%, solid waste crude oil residual quantity 1.7% (W/W).The crude oil of recycling directly weighs to calculate the rate of recovery;Oil It is measured in soil after the extraction of residual quantity organic reagent using difference weight method.
Embodiment 2
1. the culture of high efficiency flora
High efficiency flora includes Alkanindiges sp., Acinetobacter sp., Pseudomonas sp., Cupriavidus sp. and Arthrobacter sp..Nutrient solution prescription:NH4NO3,1.0g/L;Na2HPO4,1.0g/L; NaCl,0.5g/L;MgSO4,0.5g/L;CaCl2,0.05g/L;FeSO4,0.01g/L;Crude oil, 20g/L;pH 7.2.It adds in 1.0% (v/v) polysorbas20 is sufficiently stirred so that crude oil forms emulsion and evenly spreads in culture solution.It is prepared and sought with tap water Nutrient solution.Flora is cultivated in 10 liters of biological fermentation tanks, condition is as follows:35 degree of temperature, 80 revs/min of speed of agitator, aeration quantity 2 Liter/min.After culture 4 days, cell turbidity reaches 600FTU, and high efficiency flora seed liquor is spare.
It 2. will be spare after oil-mud disintegrating and the sundries such as removing stone, wooden unit, cloth, plastics and stalk that sieve;
3. the microorganism separation and recycling of greasy filth Crude Oil
Mineral nutrition liquid is prepared, formula is as follows:KNO3,0.5g/L;KH2PO4,0.5g/L;NaCl,0.25g/L; MgSO4,0.25g/L;CaCl2,0.01g/L;FeSO4,0.01g/L;pH 7.0.Crude oil is realized in 100 liters of mud reactors Microorganism separates and recycling.Mud system is formulated by oily soil and mineral nutrition liquid, mineral nutrition liquid:Oily soil ratio is 4:1 (V/V), high efficiency flora inoculum concentration 10% for the first time, 35 degree of reaction temperature, 20 liters/min of aeration quantity, 120 revs/min of speed of agitator Clock.During operation, the crude oil for once floating on liquid level is collected, and adds high efficiency flora 5% (v/v) within every two days.After operation 7 days, Crude oil adds up the rate of recovery 72%, solid waste crude oil residual quantity 2.3% (W/W).The crude oil of recycling directly weighs to calculate the rate of recovery;Oil It is measured in mud after the extraction of residual quantity organic reagent using difference weight method.
Embodiment 3
1. the culture of high efficiency flora
High effective microbial community includes Alkanindiges sp., Acinetobacter sp., Pseudomonas sp., Cupriavidus sp. and Arthrobacter sp..With oil-containing Solution culture method high efficiency flora, nutrient solution prescription:KNO3, 2.0g/L;Na2HPO4,2.0g/L;NaCl,1.0g/L;MgSO4,0.5g/L;CaCl2,0.05g/L;FeSO4,0.01g/L;It is former Oil, 30g/L;pH 7.0.It is ultrasonically treated two hours so that crude oil forms homodisperse emulsion.Nutrition is prepared with tap water Liquid.Flora is cultivated in 100 liters of aeration and biological fermentation tanks, condition is as follows:30 degree of temperature, 100 revs/min of speed of agitator, aeration 25 liters/min of amount.After culture 3 days, cell turbidity 750FTU.High efficiency flora suspension separates and recovers for follow-up crude oil.
2. oily soil is crushed and sieved and removes the sundries such as stone, wooden unit, cloth, plastics and stalk, store for future use;
3. the microorganism separation and recycling of oily soil Crude Oil
Mineral nutrition liquid is prepared, formula is as follows:KNO3,0.5g/L;NH4CI,0.5g/L;Na2HPO4,0.5g/L; KH2PO4,0.5g/L;NaCl,0.5g/L;MgSO4,0.5g/L;CaCl2,0.05g/L;FeSO4,0.05g/L;pH 7.0. The microorganism separation and recycling of crude oil are realized in 1000 liters of mud reactors.Mud system is prepared by oily soil and mineral nutrition liquid It forms, nutrient solution:Oily soil ratio is 5:1 (V/V), high efficiency flora inoculum concentration are 8.0%, and reaction temperature is 30 degree, and aeration quantity is 100 liters/min, speed of agitator is 120 revs/min.During operation, the crude oil for once floating on liquid level is collected, and is mended within every two days Add high efficiency flora 5% (v/v).After operation 5 days, crude oil adds up the rate of recovery 78%, solid waste crude oil residual quantity 1.8% (W/W).Recycling Crude oil directly weigh to calculate the rate of recovery;It is measured in greasy filth after the extraction of residual quantity organic reagent using difference weight method.
Embodiment 4
1. the culture of high efficiency flora
High effective microbial community includes Alkanindiges sp., Acinetobacter sp., Pseudomonas sp., Cupriavidus sp. and Arthrobacter sp..With oil-containing Solution culture method high efficiency flora, nutrient solution prescription:KNO3, 2.0g/L;Na2HPO4,2.0g/L;NaCl,1.0g/L;MgSO4,0.5g/L;CaCl2,0.05g/L;FeSO4,0.01g/L;It is former Oil, 30g/L;pH 7.0.It is ultrasonically treated two hours so that crude oil forms homodisperse emulsion.Nutrition is prepared with tap water Liquid.Flora is cultivated in 100 liters of aeration and biological fermentation tanks, condition is as follows:30 degree of temperature, 100 revs/min of speed of agitator, aeration 25 liters/min of amount.After culture 3 days, cell turbidity 750FTU.High efficiency flora suspension separates and recovers for follow-up crude oil.
2. by oil-mud disintegrating and the sundries such as removing stone, wooden unit, cloth, plastics and stalk that sieve, store for future use;
3. the microorganism separation and recycling of greasy filth Crude Oil
Mineral nutrition liquid is prepared, formula is as follows:KNO3,0.5g/L;NH4CI,0.5g/L;Na2HPO4,0.5g/L; KH2PO4,0.5g/L;NaCl,0.5g/L;MgSO4,0.5g/L;CaCl2,0.05g/L;FeSO4,0.05g/L;pH 7.0. The microorganism separation and recycling of crude oil are realized in 1000 liters of mud reactors.Mud system is prepared by greasy filth and mineral nutrition liquid It forms, nutrient solution:Greasy filth ratio is 5:1 (V/V), high efficiency flora inoculum concentration are 8.0%, and reaction temperature is 30 degree, and aeration quantity is 100 liters/min, speed of agitator is 150 revs/min.During operation, the crude oil for once floating on liquid level is collected, and is mended within every two days Add high efficiency flora 5% (v/v).After operation 7 days, crude oil adds up the rate of recovery 70%, solid waste crude oil residual quantity 2.5% (W/W).Recycling Crude oil directly weigh to calculate the rate of recovery;It is measured in greasy filth after the extraction of residual quantity organic reagent using difference weight method.
Embodiment 5
1. the culture of high efficiency flora
High effective microbial community includes Alkanindiges sp., Acinetobacter sp., Pseudomonas sp., Cupriavidus sp. and Arthrobacter sp..With oil-containing Solution culture method high efficiency flora, nutrient solution prescription:KNO3, 2.0g/L;Na2HPO4,2.0g/L;NaCl,1.0g/L;MgSO4,0.5g/L;CaCl2,0.05g/L;FeSO4,0.01g/L;It is former Oil, 15g/L;pH 7.0.0.75% (v/v) Tween 80 is added in be sufficiently stirred and be ultrasonically treated one hour so that crude oil forms milkiness Liquid is simultaneously evenly spread in culture solution.Nutrient solution is prepared with tap water.Flora, item are cultivated in 500 liters of aeration and biological fermentation tanks Part is as follows:35 degree of temperature, 100 revs/min of speed of agitator, 50 liters/min of aeration quantity.After culture 4 days, cell turbidity 450FTU. High efficiency flora suspension separates and recovers for follow-up crude oil.
2. oily soil is crushed and sieved and removes the sundries such as stone, wooden unit, cloth, plastics and stalk, store for future use;
3. the microorganism separation and recycling of oily soil Crude Oil
Mineral nutrition liquid is prepared, formula is as follows:KNO3,0.5g/L;NH4CI,0.5g/L;Na2HPO4,0.5g/L; KH2PO4,0.5g/L;NaCl,0.5g/L;MgSO4,0.5g/L;CaCl2,0.05g/L;FeSO4,0.05g/L;pH 7.0. The microorganism separation and recycling of crude oil are realized in 5000 liters of mud reactors.Mud system is prepared by oily soil and mineral nutrition liquid It forms, nutrient solution:Oily soil ratio is 6:1 (V/V), high efficiency flora inoculum concentration are 6.0%, and reaction temperature is 30 degree, and aeration quantity is 500 liters/min, speed of agitator is 150 revs/min.During operation, the crude oil for once floating on liquid level is collected, and is mended within every two days Add high efficiency flora 5% (v/v).After operation 7 days, crude oil adds up the rate of recovery 79%, solid waste crude oil residual quantity 1,7% (W/W).Recycling Crude oil directly weigh to calculate the rate of recovery;It is measured in greasy filth after the extraction of residual quantity organic reagent using difference weight method.

Claims (1)

1. a kind of recycle method of the crude oil so as to fulfill oil-containing dangerous waste recycling treatment using microorganism, it is characterised in that this method The step of it is as follows:
Step 1, the culture of high efficiency flora
High effective microbial community for crude oil recovery is that selection and breeding compound from the oil-polluted soils and bed mud of various regions;Bag Include 45% Alkanindiges sp., 30% Acinetobacter sp., 15% Pseudomonas sp., 5% The Arthrobacter sp. of Cupriavidus sp. and 5%;With oil-containing Solution culture method high efficiency flora, nutrient solution prescription: NH4NO3Or KNO3Or NH4CI or (NH4)2SO4, 0.4~2.0g/L;Na2HPO4Or KH2PO4, 0.4~2.0g/L;NaCl, 0.2~ 1.0g/L;MgSO4, 0.2~1.0g/L;CaCl2, 0.01~0.05g/L;FeSO4, 0.01~0.05g/L;Crude oil, 10~50g/ L;pH 6.0-8.0;Homodisperse breast is formed by being ultrasonically treated or adding in a certain amount of Tweens surfactant crude oil Turbid;Nutrient solution is prepared with distilled water or tap water;Flora is cultivated in shaking table or aeration and biological fermentation tank, condition is as follows:Temperature Spend 40-200 revs/min of 20-40 degree, shaking table or speed of agitator, 0.1-0.5 times of nutrient solution volume/minute of aeration quantity;Culture is about After 2-4 days, cell growth reaches stationary phase, cell turbidity 300-1200FTU;High efficiency flora suspension is for oil-containing dangerous waste Crude Oil Microorganism separates and recycling;
Stone, wooden unit, cloth, plastics and stalk are removed Step 2: crushing and sieving oily soil, greasy filth, bed mud oil-containing dangerous waste Sundries stores for future use;
Step 3: the microorganism separation and recycling of oil-containing dangerous waste Crude Oil
Mineral nutrition liquid is prepared, formula is as follows:NH4NO3Or KNO3Or NH4CI or (NH4)2SO4, 0.1~1.0g/L;Na2HPO4 Or KH2PO4, 0.1~1.0g/L;NaCl, 0.1~0.5g/L;MgSO4, 0.1~0.5g/L;CaCl2, 0.01~0.05g/L; FeSO4, 0.01~0.05g/L;pH 6.0-8.0;In mud reactor realize oil-containing dangerous waste Crude Oil microorganism separation and Recycling;Mud system is formulated by a certain percentage by oil-containing dangerous waste and mineral nutrition liquid, mineral nutrition liquid:Oil-containing dangerous waste Volume ratio be 3:1-6:1, high efficiency flora inoculum concentration be 2%-10%, reaction temperature be 20-40 degree, aeration quantity 0.05- 0.5 times of nutrient solution volume/minute, speed of agitator are 40-200 revs/min;After operation 3-9 days, oil-containing dangerous waste Crude Oil and substrate It separates and acts on float downward to reactor liquid level in aeration, crude oil recovery rate 60-90%, the quality residual quantity of dangerous waste crude oil is 0.5-3.0%;Operational process regards flora growth situation and suitably supplements the volume ratio of microbial inoculum as 2%-10%.
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