CN105967343A - Compound biological enzyme preparation, compound microbial agent and application thereof in treatment of oily sludge - Google Patents

Compound biological enzyme preparation, compound microbial agent and application thereof in treatment of oily sludge Download PDF

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CN105967343A
CN105967343A CN201610307261.7A CN201610307261A CN105967343A CN 105967343 A CN105967343 A CN 105967343A CN 201610307261 A CN201610307261 A CN 201610307261A CN 105967343 A CN105967343 A CN 105967343A
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bacillus
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ferment
biological enzyme
enzyme preparation
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CN105967343B (en
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陈五岭
杜茂林
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Shaanxi Wenling Microbiology Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/342Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/347Use of yeasts or fungi
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    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/14Fungi; Culture media therefor
    • C12N1/16Yeasts; Culture media therefor
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    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20Bacteria; Culture media therefor
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/32Hydrocarbons, e.g. oil
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

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Abstract

The invention provides a compound biological enzyme preparation, a compound microbial agent and application thereof in the treatment of oily sludge. The compound biological enzyme preparation is prepared from bacillus subtilis, bacillus pumilus, candida and lactobacillus brevis. The compound microbial agent is prepared from candida tropicalis, sphingobacterium multivolume, bacillus cereus, acinetobacter calcoaceticus and bacillus megaterium. The invention also provides the application of the compound biological enzyme preparation and / or the compound microbial agent in the treatment of oily sludge and a method for treating the oily sludge. The method comprises steps of treating the oily sludge with the compound biological enzyme preparation to form an upper oil phase, an intermediate aqueous phase and a lower sludge phase, and treating the lower sludge phase and / or the intermediate aqueous phase by using the composite microbial agent. The compound biological enzyme preparation, the compound microbial agent and the application thereof provided by the invention have the advantages of harmless treatment of oily sludge, low cost, simplicity and convenience, no secondary pollution, and broad application prospects.

Description

Composite biological enzyme preparation, complex micro organism fungicide and the application in disposal of oily sludge thereof
Art
The invention belongs to Environment protection of oil field technical applications, relate to the treatment technology of oily sludge, more specifically, this The bright biologic treating technique relating to oily sludge, in particular for processing composite biological enzyme preparation and the complex microorganism of oily sludge Microbial inoculum and the application in oily sludge thereof.
Background technology
Oily sludge is that a class mostlys come from oil-gas mining, oil field gathering and transportation, oil plant and the generation of oil-polluted water disposal process The suspension emulsion system that composition is extremely complex, disposes and is not good to environment structure grave danger.Process the most both at home and abroad containing greasy dirt The method of mud generally comprises: burning method, hot washing method, solvent extraction, chemical demulsification method, solid-liquid isolation method, pyrogenic process, Reuse profile controls etc., though these methods can reduce the oily sludge harm to environment to a certain extent, but remain in some problems, as Burning method power consumption is big, be easily generated secondary pollution, and crude oil cannot recycle;Solvent extraction complex process, processing cost is high, Only the oily sludge containing a large amount of hardly degraded organic substances is suitable for, is difficult to large-scale promotion and uses.At present biological method the most gradually by In the disposal process of application and oily sludge, as CN201410623397.X provides a kind of disposal of oily sludge medicament and system thereof Standby, using method, adds to containing greasy dirt after surfactant, calcium chloride, the compounding suitably dilution of propylene glycol including by enzyme Mud, and stir 10-20min with 200-300r/min rotating speed.Utilize the method to process oily sludge, use chemistry completely though can reduce Demulsifier processes the secondary harm that oily sludge brings to environment, but still be difficult to the mud crude content after overcoming process higher and The defect that harmful components are difficult to substantially remove.CN201210180830.8 provides a kind of Microbiological oil sludge treatment technique, this technique Including greasy filth fluidization, biological treatment, sludge dewatering and four steps of biotic induce, described biological treatment step is to biology Retort adds Candida lipolytica Y-57 and pseudomonas putida P-101, after aeration and biological reacts, oil in terms of over dry mud Mud oil-containing is less than 2%, and water oil-containing is less than 150mg/L;On water surface top, oil slick is recycled by oil-collecting device, the thin mud in bottom Husky standard discharge, greasy filth enters sludge dewatering step.Although the method can show the crude content reducing mud, but there is technique Complicated and be difficult to remove the defect of other harmful components of oily sludge, and simple bioanalysis can only process the relatively low greasy filth of oil content and Process time-consuming long.
Therefore, the art is highly desirable to provide a kind of one or more problems above-mentioned that can overcome existing for prior art Process for treating oil-containing sludge.
Summary of the invention
The present invention provides a kind of method for processing oily sludge in first aspect, and described method comprises the steps:
(1) use composite biological enzyme preparation to process oily sludge, form upper oil phase, intermediate layer aqueous phase and lower floor's mud phase;With
(2) complex micro organism fungicide is used to process described lower floor mud phase and/or described intermediate layer aqueous phase.
The present invention provides a kind of composite biological enzyme preparation in second aspect, described composite biological enzyme preparation prepared by following strain and/ Or comprise following strain: bacillus subtilis (Bacillus subtilis), Bacillus pumilus (Bacillus pumilus), false silk Yeast (Candida Albicans) and Lactobacillus brevis (Lactobacillus breris).
The present invention provides a kind of complex micro organism fungicide in the third aspect, described complex micro organism fungicide prepared by following strain and/ Or comprise following strain: candida tropicalis (Candida tropicalis), Sphingobacterium multivorum (Sphingobacterium Multivolum), Bacillus cercus (Bacillus cereus), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus) and huge Bacterium anthracoides (Bacillus megaterium).
The present invention provides the composite biological enzyme preparation described in second aspect present invention and/or third aspect present invention institute in fourth aspect The complex micro organism fungicide stated application in processing oily sludge, the especially compound biological enzyme system described in second aspect present invention The complex micro organism fungicide described in agent and third aspect present invention combination application in processing oily sludge.
The present invention utilizes composite biological enzyme preparation and complex micro organism fungicide integrated treatment oily sludge, first with compound biological enzyme Crude oil in preparation separation oily sludge and other solid liquid phases such as mud phase and aqueous phase, then utilize complex microorganism preparations to enter one Step processes other solid liquid phases that oil content is relatively low, to reach crude oil recovery, the effect of greasy filth harmless treatment.The present invention can have Imitate the recovery crude oil solving oily sludge and the problem that ecological environment of soil is worked the mischief thereof, by the technology of the present invention to dirty The ecological environment of dye carries out biological restoration, can recover contaminated ecological environment, with low cost, and flow process is simple, and can enable Source exploitation is organically merged with environmental conservation, meets the strategy and policy of national sustainable development.And, the present invention can be to oil-containing Mud carries out simply and efficiently processing and not having secondary pollution, and application prospect is boundless.
Detailed description of the invention
As it has been described above, the present invention provides a kind of method for processing oily sludge in first aspect, described method includes as follows Step:
(1) use composite biological enzyme preparation to process oily sludge, form upper oil phase, intermediate layer aqueous phase and lower floor's mud phase;With
(2) complex micro organism fungicide is used to process described lower floor mud phase and/or described intermediate layer aqueous phase.
Some preferred embodiment in, described composite biological enzyme preparation is by bacillus subtilis (Bacillus subtilis), short Bacillus pumilus (Bacillus pumilus), candida mycoderma (Candida Albicans) and Lactobacillus brevis (Lactobacillus breris) Prepare, or comprise bacillus subtilis (Bacillus subtilis), Bacillus pumilus (Bacillus pumilus), false silk Yeast (Candida Albicans) and Lactobacillus brevis (Lactobacillus breris).It is a discovery of the invention that described compound biological enzyme The described strain of preparation can utilize crude oil to mushroom out breeding as sole nutrition source, and its metabolic activity can make in crude oil The macromolecules degradations such as Colophonium, waxiness, colloid, make viscosity of crude reduce, significantly improve the emulsifiability of oily sludge.Described multiple The described strain closing biological enzyme formulation is known, such as can be commercially available from Zi Rui bio tech ltd, Xi'an.
In the most preferably some embodiments, described complex micro organism fungicide is by candida tropicalis (Candida Tropicalis), Sphingobacterium multivorum (Sphingobacterium multivolum), Bacillus cercus (Bacillus cereus), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus) and bacillus megaterium (Bacillus megaterium) prepare, and/ Or comprise candida tropicalis (Candida tropicalis), Sphingobacterium multivorum (Sphingobacterium multivolum), Bacillus cercus (Bacillus cereus), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus) and bacillus megaterium (Bacillus megaterium).The described strain of described complex micro organism fungicide is known, such as can be from the Xi'an auspicious biology of purple Science and Technology Ltd. is commercially available.
The inventors discovered that, the described strain of described complex micro organism fungicide all sees the drilling well waste liquid of domestic each elephant, adopts In water outlet and all kinds of oily sludge, and oily sludge main harm composition of can effectively degrading, wherein:
Described candida tropicalis can utilize the Hydrocarbon conducts such as the normal alkane in crude oil fraction, positive alkene and cycloalkane Carbon source needed for growth, the hydrocarbon compound in water can be emulsified into profit be sufficiently mixed by producing lipoprotein emulsifying agent by it Droplet, can directly be utilized for thalli growth and metabolism;
Described Sphingobacterium multivorum contains the dioxygenase system relevant with degrading polycyclic aromatic hydrocarbons, can preferably utilize many cyclophanes Hydrocarbon, polycyclic aromatic hydrocarbon Transport And Transformation so that final disappear from environment during play a significant role;
Described Bacillus cercus heavy metal has stronger resistance, plays in remediating heavy metal and PBDE combined pollution Important function, has good degradation effect to the macromolecule carbochain (such as paraffin, Colophonium etc.) in crude oil;
Described Acinetobacter calcoaceticus has stronger reducing crude oil surface tension and decompose the ability of emulsifying utilization of can degrading Long chain alkane, polycyclic aromatic hydrocarbon, phenols etc., it is possible to phenol for growth needed for sole carbon source, there is efficient degradation phenol, benzene The ability of formic acid and catechol etc.;
Described bacillus megaterium can significantly be degraded the polycyclic aromatic hydrocarbon in environment, and it is sent out during Cd contaminated soil remediation Wave important function, the advantage such as additionally have that nutritional requirement is low and growth is fast.
In some further preferred embodiments, described biological enzyme formulation prepares in the following way:
I described bacillus subtilis, Bacillus pumilus, candida mycoderma and Lactobacillus brevis are prepared as solid fungicide by () respectively; With
(ii) by the solid of prepared for step (i) described bacillus subtilis, Bacillus pumilus, candida mycoderma and Lactobacillus brevis Microbial inoculum mixes and carries out ferment tank, thus prepares described complex microorganism preparations.
In the most preferred embodiment, described biological enzyme formulation prepares in the following way:
(i) by described bacillus subtilis, Bacillus pumilus and candida mycoderma respectively through slant culture, shake-flask culture and once Ferment tank is cultivated, and then using the mixture of wheat bran and water as culture medium, prepares described bacillus subtilis, short and small respectively Bacillus cereus, the solid fungicide of candida mycoderma;Described Lactobacillus brevis is carried out liquid static anaerobism amplification culture step by step, then with The mixture of Semen Maydis powder and water, as culture medium, prepares the solid fungicide of described Lactobacillus brevis;
(ii) solid fungicide of described bacillus subtilis, Bacillus pumilus, candida mycoderma and Lactobacillus brevis is mixed, obtain Solid composite bacteria agent capable, accesses described solid composite bacteria agent capable in fermentation substrate and uses carbamide to regulate carbon-nitrogen ratio, stirring laggard Row ferment in second time tank ferments, and prepares the fermentation liquid for described composite biological enzyme preparation.
The slant culture of described bacillus subtilis, Bacillus pumilus and candida mycoderma, shake-flask culture and the fermentation of one time fermentation tank Cultivate and the Anaerobic culturel of described Lactobacillus brevis is well known in the art, such as: cultivate bacillus subtilis and short and small Used by potato culture, cultivation Lactobacillus brevis used by beef-protein medium, cultivation candida mycoderma used by bacillus cereus MRS culture medium, can be the most commercially available from Zi Rui bio tech ltd, Xi'an.In some embodiments, described inclined-plane The temperature cultivated is 28-35 DEG C, and incubation time is 48 hours;Temperature 28-35 DEG C of described shake-flask culture, shaking speed controls At 160-180r/min, cultivate 48 hours;The temperature of described fermentor cultivation controls at 28-35 DEG C, cultivates about 48 hours;Short Lactobacillus uses the static Anaerobic culturel of liquid step by step, and cultivation temperature controls at 35-40 DEG C, cultivates about 48 hours.
Each culture medium particular make-up can be:
Beef-protein medium (g/L): Carnis Bovis seu Bubali cream 3, peptone 10, NaCl 5 (solid medium need to add 1.5% agar);
Potato culture (g/L): Rhizoma Solani tuber osi 200, sucrose 20 (solid medium need to add 1.5% agar);
MRS culture medium (g/L): peptone 10.0, beef extract powder 8.0, yeast leaching powder 4.0, glucose 20.0, phosphoric acid hydrogen two Potassium 2.0, diammonium hydrogen citrate 2.0, sodium acetate 5.0, magnesium sulfate 0.2, manganese sulfate 0.04, Tween 80 1.0.
In more preferred embodiments, the wheat bran in the mixture of the ferment in second time tank wheat bran that used of fermentation and water and water Mass ratio be 1:1, it is further preferred that, wheat bran has the granularity of 1mm to 5mm, such as 1,2,3,4 or 5mm Granularity.Semen Maydis in more preferred embodiments, in the Semen Maydis powder of ferment in second time tank fermentation use and the mixture of water The mass ratio of powder and water is 5:4, it is further preferred that, Semen Maydis powder has a granularity of 1mm to 2mm, for example, 1,1.5, The granularity of 2mm.In some embodiments, the described bacillus subtilis in solid composite bacteria agent capable, Bacillus pumilus, vacation The mass ratio of the solid fungicide of silk yeast and Lactobacillus brevis is 2:2:2:1.
Some preferred embodiment in, ferment in second time tank fermentation described fermentation substrate be marc, preferably Fructus Mali pumilae and/or Mi Monkey peach fruit slag, it is further preferred that the granularity of described fermentation substrate is 1cm to 2cm, the granularity of for example, 1,1.5 or 2cm. In some embodiments, in terms of the gross mass of described fermentation substrate, the amount of the described solid composite bacteria agent capable of access is 1 mass %. In other embodiment, in terms of the gross mass of described fermentation substrate, the amount of the described carbamide for regulating carbon-nitrogen ratio is 0.5 Quality %.Some preferred embodiment in, ferment in second time tank fermentation obtained by described fermentation liquid be ferment in second time tank fermentation The liquid phase that gained material obtains through solid-liquid separation.Some preferred embodiment in, ferment in second time tank fermentation enter in ambient temperature Row 20 days to 35 days;Also it is preferred that the fermentation of ferment in second time tank is fermented 10 days to 15 days at 30 DEG C.Preferred at some In embodiment, the fermentation of ferment in second time tank is with when 40 DEG C, and 1mL fermentation liquid can be catalyzed 100mL crude oil standard substance emulsifying for sending out Ferment terminal, described crude oil standard substance are the crude oil mark product with volume ratio as 7:3 and the mixture of water.
In some embodiments, described candida tropicalis, Sphingobacterium multivorum, Bacillus cercus, calcium acetate are motionless Bacillus and bacillus megaterium are cultivated through slant culture, shake-flask culture and ferment tank successively, then with wheat bran and the mixing of water Thing, as culture medium, makes the solid fungicide of each described strain and is mixed to form described complex micro organism fungicide.The false silk in the described torrid zone Yeast, Sphingobacterium multivorum, Bacillus cercus, Acinetobacter calcoaceticus and bacillus megaterium successively through slant culture, Shake-flask culture and ferment tank are cultivated and are well known in the art such as: cultivate Sphingobacterium multivorum, Bacillus cercus, Rhizoma Solani tuber osi training used by beef-protein medium, cultivation candida tropicalis used by Acinetobacter calcoaceticus and bacillus megaterium Foster base can be the most commercially available from Zi Rui bio tech ltd, Xi'an.In some embodiments, the temperature of described slant culture Degree is for 28-35 DEG C, and incubation time is 48 hours;Temperature 28-35 DEG C of described shake-flask culture, shaking speed controls 160-180r/min, cultivates 48 hours;The temperature of described fermentor cultivation controls at 28-35 DEG C, cultivates about 48 hours.
In some embodiments, described candida tropicalis, Sphingobacterium multivorum, Bacillus cercus, calcium acetate are motionless The solid fungicide of bacillus and bacillus megaterium mixes with the mass ratio of 1:2:2:1:1.Also it is preferred that wheat bran and the mixing of water Wheat bran and the mass ratio of water in thing are 1:1.
In some embodiments, in step (1), composite biological enzyme preparation is configured to the aqueous solution of 1 mass %, according to oil-containing The mass ratio 2:0.5-1 (for example, 2:05,2:0.6,2:0.7,2:0.8,2:0.9 or 2:1.0) of mud and described aqueous solution adds Enter in oily sludge and stir, being heated to 50 DEG C, standing 1 hour to form upper oil phase, intermediate layer aqueous phase and lower floor Mud phase, is evacuated to upper oil phase oil water separator process and reclaims, intermediate layer aqueous phase return is processed pond and reuses institute State composite biological enzyme preparation to repeat to process 2 to 3 times or till no longer having crude oil to wash out.About oily sludge and described water The mass ratio of solution, those skilled in the art can exist regarding the initial moisture content of oily sludge according to content disclosed in this specification Be determined in the range of described, such as, when the initial moisture content of oily sludge is high, the accounting of the oily sludge in described mass ratio Can be larger, smaller.
In some embodiments, in step (2), the oily sludge of gained accesses in step (1) 2% (mass body Long-pending than) complex micro organism fungicide and stir, material removal is processed pond, heap fermentation 30 to 45 days.
In the embodiment that some are more specific, described bacillus subtilis, Bacillus pumilus, candida mycoderma can be divided Not after slant culture, shake-flask culture and one time fermentation tank fermentation culture with wheat bran (wheat bran: water=1:1) as culture medium, in making State the solid fungicide of bacterial strain.Lactobacillus brevis is anaerobe, step by step with Semen Maydis powder (Semen Maydis powder: water after liquid static anaerobism amplification culture =5:4) it is culture medium, make solid fungicide;With marc as fermentation substrate, access the 1% micro-life of above-mentioned mixing according to 2:2:2:1 ratio Thing solid fungicide, is concurrently accessed the carbamide regulation carbon-nitrogen ratio of 0.5%, enters tank or pond fermentation after fully mixing thoroughly.Preferably apple, macaque Fructus Persicae and leftover bits and pieces thereof are as fermentation substrate, and wherein bulk can be pulverized as using after granularity about 1-2cm by size-reduced machine.Fermentation can be certainly So carry out under state, it is also possible to according to the length of ambient temperature different adjustment fermentation time.Under ambient temperature conditions, fermentation one As need continue 20 to 35 days.In preferably some embodiments, continuing fermentation 10 days to 15 days in 30 DEG C of fermentation tanks.Described Composite biological enzyme preparation is mainly by protease produced during described complex microbial community growth metabolism, lipase and sugar Fat, phospholipid, lipopeptid and lipoprotein metabolism product are constituted.During fermentation can with 40 DEG C time, it is former that 1mL fermentation liquid can be catalyzed 100mL Oil standard product (crude oil mark product: water=7:3) are fully emulsified for fermentation termination.After fermentation completes, by fermentation liquid with 5000g centrifugal force Centrifugal 10min, obtains composite biological enzyme preparation.
In the embodiment that some are more specific, use described composite biological enzyme preparation process oily sludge time, can first by Composite biological enzyme preparation is configured to the aqueous solution of 1 mass %, adds according to the mass ratio 2:0.5-1 of oily sludge and described aqueous solution In oily sludge, utilize blender uniform stirring 10 minutes, be heated to 50 DEG C, stand 1 hour.Then treat that profit mud divides From, upper strata oil slick being evacuated to oil water separator and processes, oil phase is reclaimed, aqueous phase liquid can return to process pond Reusability, this mistake Journey can be repeated 2 to 3 times, or till no longer having crude oil to wash out, follow-up access microorganism treated by gained material.
In the embodiment that some are more specific, by described candida tropicalis, Sphingobacterium multivorum, wax-like spore bar Bacterium, Acinetobacter calcoaceticus, bacillus megaterium successively through slant culture, shake-flask culture and ferment tank cultivate after with wheat bran (wheat bran: water=1:1) is culture medium, makes solid fungicide and mixes according to 1:2:2:1:1 ratio, preparing complex micro organism fungicide. Then described complex micro organism fungicide is used to process oily sludge.Specifically, to the oily sludge cleaned via biological enzyme formulation (can include that intermediate layer aqueous phase can not also include intermediate layer aqueous phase) is accessed the compound micro-of 2% (mass volume ratio, kg/L) Bacteria agent, stirs, and removal processes pond, heap fermentation 30 to 45 days.
The present invention additionally provides a kind of composite biological enzyme preparation in second aspect, and described composite biological enzyme preparation is by bacillus subtilis (Bacillus subtilis), Bacillus pumilus (Bacillus pumilus), candida mycoderma (Candida Albicans) and short breast Bacillus (Lactobacillus breris) prepares.Present invention also offers the method preparing described composite biological enzyme preparation, specifically side Method may refer to, described in first aspect present invention, not repeat them here.
The present invention provides a kind of complex micro organism fungicide in the third aspect, and described complex micro organism fungicide is by candida tropicalis (Candida tropicalis), Sphingobacterium multivorum (Sphingobacterium multivolum), Bacillus cercus (Bacillus Cereus), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus) and bacillus megaterium (Bacillus megaterium) system ?.Present invention also offers the method preparing described complex micro organism fungicide, concrete grammar may refer to first aspect present invention institute State, do not repeat them here.
The composite biological enzyme preparation that fourth aspect present invention additionally provides described in second aspect present invention is processing or pretreatment oil-containing Application in mud.Present invention also offers the complex micro organism fungicide described in third aspect present invention processing or locating further Application in reason oily sludge.Present invention also offers the composite biological enzyme preparation described in second aspect present invention and/or the present invention The complex micro organism fungicide described in three aspects combination application in processing oily sludge.
According to the present invention, use described composite biological enzyme preparation to clean and described complex micro organism fungicide processes oily sludge, its stone Petroleum hydrocarbon clearance can reach more than 95%, and pH value is down to 6.5-7.5, and volatile phenol, total cyanogen compound and content of beary metal are notable Reduce, really realize the harmlessness disposing of oily sludge.
Embodiment
Hereafter by the way of embodiment, the present invention will be described further, but the present invention is not limited to such reality Execute example.
Detailed description of the invention:
Embodiment 1
1, test objective:
The centrifugation that oily sludge Crude Oil is produced by research composite biological enzyme preparation with mud, and utilize complex micro organism fungicide to enter One step process greasy filth to reach crude oil recovery, the effect of greasy filth harmless treatment.
2, test material:
2.1 oily sludges: CNOOC's greasy filth.
The preparation of 2.2 composite biological enzyme preparation
Bacillus subtilis (Bacillus subtilis), Bacillus pumilus (Bacillus pumilus), candida mycoderma (Candida Albicans), to be purchased from the purple auspicious biotechnology in Xi'an limited for Lactobacillus brevis (Lactobacillus breris) and culture medium used thereof Company.Wherein, cultivate bacillus subtilis and Bacillus pumilus uses beef-protein medium, cultivates candida mycoderma Use potato culture, cultivate Lactobacillus brevis use MRS culture medium.The composition of culture medium is as follows:
Beef-protein medium (g/L): Carnis Bovis seu Bubali cream 3, peptone 10, NaCl 5 (solid medium need to add 1.5% agar);
Potato culture (g/L): Rhizoma Solani tuber osi 200, sucrose 20 (solid medium need to add 1.5% agar);
MRS culture medium (g/L): peptone 10.0, beef extract powder 8.0, yeast leaching powder 4.0, glucose 20.0, phosphoric acid hydrogen two Potassium 2.0, diammonium hydrogen citrate 2.0, sodium acetate 5.0, magnesium sulfate 0.2, manganese sulfate 0.04, Tween 80 1.0.
By above-mentioned bacillus subtilis, Bacillus pumilus, candida mycoderma respectively through slant culture (30 DEG C, cultivate 48 hours), Shake-flask culture (30 DEG C, rotating speed 180r/min, cultivate 48 hours) and one time fermentation tank fermentation culture (30 DEG C, cultivate 48 hours) After, fully mix thoroughly as culture medium with wheat bran (wheat bran: water=1:1), 30 DEG C of fermentations reach 10 to viable count in about 48 hours8CFU/mL with On be the solid fungicide of above-mentioned bacterial strains.
Lactobacillus brevis is anaerobe, static through shaking flask (37 DEG C, 48 hours) and fermentation tank (37 DEG C, 48 hours) liquid step by step With Semen Maydis powder (Semen Maydis powder: water=5:4) as culture medium after anaerobism amplification culture, 37 DEG C of cultivations reach 10 to viable count in about 48 hours8 More than CFU/mL is Lactobacillus brevis solid fungicide.
With the pomace of the granularity with 1cm as fermentation substrate, according to 2:2:2:1 ratio by bacillus subtilis (Bacillus Subtilis), Bacillus pumilus (Bacillus pumilus), candida mycoderma (Candida Albicans), Lactobacillus brevis The solid fungicide mixing of (Lactobacillus breris), and in terms of the quality of fermentation substrate, access the 1 above-mentioned mixing of mass % micro- Biosolids microbial inoculum, is concurrently accessed the carbamide regulation carbon-nitrogen ratio of 0.5 mass %, loads ferment tank after fully mixing thoroughly.Ferment In 30 DEG C of fermentation tanks, continuing fermentation 15 days, obtains fermentation liquid, and when 40 DEG C, fermentation liquid described in 1mL can be catalyzed 100mL crude oil mark Quasi-product (crude oil mark product: water=7:3) emulsifying completely.After fermentation completes, by fermentation liquid with 5000g centrifugal force 10min, i.e. The liquid phase part of described composite biological enzyme preparation must be can serve as.
The preparation of 2.3 complex micro organism fungicides
Described candida tropicalis (Candida tropicalis), Sphingobacterium multivorum (Sphingobacterium multivolum), Bacillus cercus (Bacillus cereus), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus), bacillus megaterium Culture medium used by (Bacillus megaterium) and cultivation is purchased from Zi Rui bio tech ltd, Xi'an.Wherein, cultivation is many Food Sphingobacterium, Bacillus cercus, Acinetobacter calcoaceticus and bacillus megaterium use beef-protein medium, And cultivate candida tropicalis and use potato culture.The composition of culture medium is as follows:
Beef-protein medium (g/L): Carnis Bovis seu Bubali cream 3, peptone 10, NaCl 5 (solid medium need to add 1.5% agar);
Potato culture (g/L): Rhizoma Solani tuber osi 200, sucrose 20 (solid medium need to add 1.5% agar).
By above-mentioned candida tropicalis, Sphingobacterium multivorum, Bacillus cercus, Acinetobacter calcoaceticus, huge spore bar Bacterium is successively through slant culture (30 DEG C, 48 hours), shake-flask culture (30 DEG C, 180r/min, 48 hours) and ferment tank As culture medium, fully mix thoroughly with wheat bran (wheat bran: water=1:1) after cultivating (30 DEG C, 48 hours), cultivate about 48 hours extremely for 30 DEG C Viable count reaches 108More than CFU/mL i.e. obtains corresponding solid fungicide, and is mixed and stirred for uniformly according to the mass ratio of 1:2:2:1:1, system Obtain described complex micro organism fungicide.
3, test procedure:
Experimental group: take 1000g CNOOC greasy filth sample and put in 2000mL beaker, adds 500mL, the described compound bio of 1% Enzyme preparation, rises to temperature 50 DEG C and is sufficiently stirred for about 10 minutes, stands, and reaches the separating effect of oil and mud;Reclaim beaker The upper oil phase (crude oil phase) on surface, is placed on another beaker and preserves;By 2% (mass/volume) in greasy filth after recovery Adding complex microorganism strain and stir, then removal processes pond, heap fermentation 45 days
The oily sludge of matched group does not use composite biological enzyme preparation and complex micro organism fungicide to process, and only adds 500mL Distilled water, and place 45 days after removing the oil slick that surface is a small amount of and detect index of correlation.
4, result of the test:
The physical and chemical factors such as its petroleum hydrocarbon of oily sludge through composite biological enzyme preparation and complex micro organism fungicide integrated treatment and a huge sum of money Belonging to content to carry out according to reference to GB 18598-2001 and HJT 166 2004, result is as shown in table 1, table 2.
Table 1 CNOOC oily sludge leachate physical and chemical factor detection data
/ expression does not detects.
Table 2 CNOOC oily sludge leachate content of beary metal detection data
Matched group Experimental group
Copper (in terms of Cu, mg/kg) 7.97 1.25
Zinc (in terms of Zn, mg/kg) 9.94 3.22
Cadmium (in terms of Cd, mg/kg) 0.1 0.05
Lead (in terms of Pb, mg/kg) 1.67 0.62
Chromium (in terms of Cr, mg/kg) 4.76 2.75
Hydrargyrum (in terms of Hg, mg/kg) 0.02 < 0.01
Arsenic (in terms of As, mg/kg) 0.82 0.15
Selenium (in terms of Se, mg/kg) / /
/ expression does not detects.
From table 1, table 2, treated oily sludge petroleum hydrocarbon and other harmful substance contents all significantly reduce, and show the party Method high treating effect, achieves oily sludge harmless treatment standard substantially.
Embodiment 2
1, test objective
Middle Oil Safety environmental protection academy and North China Oilfield mutual authentication oily sludge compound biological enzyme and microbial method integrated treatment skill Art is to the popularization feasibility of the construction technology of oily sludge and oily sludge harmless treatment effect.
2, test material
2.1 North China Oilfield greasy filth;
The preparation of 2.2 composite biological enzyme preparation
Use the described composite biological enzyme preparation obtained by embodiment 1.
The preparation of 2.3 complex micro organism fungicides.
Use the described complex micro organism fungicide obtained by embodiment 1.
3, test procedure
This experiment every batch processing oily sludge amount is 5t (ton).
(1) test is undertaken in two steps:
A. utilize composite biological enzyme preparation that oily sludge Crude Oil and Colophonium, waxiness etc. are separated eluting.
B. utilize complex micro organism fungicide that residue silt is carried out harmlessness disposing.
(2) technological process:
Experimental group: add 1% composite biological enzyme preparation 2t, oily sludge 5t to processing in pond, utilize blender uniform stirring 10 Minute, it is heated to 50 DEG C, stands 1 hour.Treat Oil Water Sludge Separation, upper strata oil slick is evacuated to oil water separator and processes, oil is entered Row reclaims, and aqueous phase liquid return processes pond Reusability, and this process can be repeated 3 times until processing in pond without big quantity of fluid. Stirring after residue silt and liquid add 2% (mass/volume) complex micro organism fungicide, removal processes pond and piles up Fermentation is to carry out harmless treatment.After 30 days, environmental administration and oil field relevant departments use side same as in Example 1 Method detection all technical, carries out on-the-spot Acceptance test.
The oily sludge of matched group does not use composite biological enzyme preparation and complex micro organism fungicide to process, sampling inspection after 30 days Survey.
4, result of the test
Table 3 CNOOC oily sludge leachate physical and chemical factor detection data
Table 4 CNOOC oily sludge leachate content of beary metal detection data
After testing, the composite biological enzyme preparation of the present invention and the oily sludge crude oil recovery of complex micro organism fungicide integrated treatment are utilized Rate reaches 87%, and removal rate of petroleum hydrocarbons is up to more than 99%.Silt after process returns to national II class Soil standard (GB 15618—2008)。

Claims (10)

1. the method being used for processing oily sludge, it is characterised in that described method comprises the steps:
(1) use composite biological enzyme preparation to process oily sludge, form upper oil phase, intermediate layer aqueous phase and lower floor's mud phase;
(2) complex micro organism fungicide is used to process described lower floor mud phase and/or described intermediate layer aqueous phase.
Method the most according to claim 1, it is characterised in that described composite biological enzyme preparation by following strain prepare and/ Or comprise following strain: bacillus subtilis (Bacillus subtilis), Bacillus pumilus (Bacillus pumilus), false silk Yeast (Candida Albicans) and Lactobacillus brevis (Lactobacillus breris).
Method the most according to claim 1 and 2, it is characterised in that described complex micro organism fungicide is prepared by following strain Or comprise following strain: candida tropicalis (Candida tropicalis), Sphingobacterium multivorum (Sphingobacterium Multivolum), Bacillus cercus (Bacillus cereus), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus) and huge Bacterium anthracoides (Bacillus megaterium).
The most according to the method in any one of claims 1 to 3, it is characterised in that described biological enzyme formulation is by such as lower section Formula prepares:
I described bacillus subtilis, Bacillus pumilus, candida mycoderma and Lactobacillus brevis are prepared as solid fungicide by () respectively; With
(ii) by the solid of prepared for step (i) described bacillus subtilis, Bacillus pumilus, candida mycoderma and Lactobacillus brevis Microbial inoculum mixes and carries out ferment tank, thus prepares described complex microorganism preparations.
Method the most according to claim 4, it is characterised in that described biological enzyme formulation prepares in the following way:
(i) by described bacillus subtilis, Bacillus pumilus and candida mycoderma respectively through slant culture, shake-flask culture and once Ferment tank is cultivated, and then using the mixture of wheat bran and water as culture medium, prepares described bacillus subtilis, short and small respectively Bacillus cereus, the solid fungicide of candida mycoderma;Described Lactobacillus brevis is carried out liquid static anaerobism amplification culture step by step, then with The mixture of Semen Maydis powder and water, as culture medium, prepares the solid fungicide of described Lactobacillus brevis;
(ii) solid fungicide of described bacillus subtilis, Bacillus pumilus, candida mycoderma and Lactobacillus brevis is mixed, obtain Solid composite bacteria agent capable, accesses described solid composite bacteria agent capable in fermentation substrate and uses carbamide to regulate carbon-nitrogen ratio, stirring laggard Row ferment in second time tank ferments, and prepares the fermentation liquid for described composite biological enzyme preparation.
Method the most according to claim 5, it is characterised in that:
Wheat bran and the mass ratio of water in the wheat bran of described ferment in second time tank fermentation use and the mixture of water are 1:1, it is further preferred that Wheat bran has the granularity of 1mm to 5mm;
Semen Maydis powder and the mass ratio of water in the Semen Maydis powder of described ferment in second time tank fermentation use and the mixture of water are 5:4, more preferably , Semen Maydis powder has the granularity of 1mm to 2mm;
Described bacillus subtilis in the solid composite bacteria agent capable that the fermentation of described ferment in second time tank uses, Bacillus pumilus, false silk The mass ratio of the solid fungicide of yeast and Lactobacillus brevis is 2:2:2:1;
The described fermentation substrate that the fermentation of described ferment in second time tank uses is marc, preferably Fructus Mali pumilae and/or Chinese gooseberry pomace, more preferably Be the granularity of described fermentation substrate be 1cm to 2cm;
In terms of the gross mass of described fermentation substrate, the amount of the described solid composite bacteria agent capable that the fermentation of described ferment in second time tank accesses is 1 matter Amount %;
In terms of the gross mass of described fermentation substrate, the amount of described carbamide being used for regulating carbon-nitrogen ratio in the fermentation of described ferment in second time tank is 0.5 mass %;
The described fermentation liquid that the fermentation of described ferment in second time tank obtains is the liquid that ferment in second time tank fermentation gained material obtains through solid-liquid separation Phase;And/or
Described ferment in second time tank fermentation carry out 20 days to 35 days in ambient temperature, it is additionally preferred be 30 DEG C fermentation 10 days extremely 15 days;And/or
The fermentation of ferment in second time tank is with when 40 DEG C, and it is fermentation termination that 1mL fermentation liquid can be catalyzed 100mL crude oil standard substance emulsifying, Described crude oil standard substance are the crude oil mark product with volume ratio as 7:3 and the mixture of water.
Method the most according to claim 3, it is characterised in that described candida tropicalis, Sphingobacterium multivorum, wax Shape bacillus cereus, Acinetobacter calcoaceticus and bacillus megaterium are cultivated through slant culture, shake-flask culture and ferment tank successively, Then using the mixture of wheat bran and water as culture medium, make the solid fungicide of each described strain and be mixed to form described composite microbial Thing microbial inoculum.
Method the most according to claim 7, it is characterised in that described candida tropicalis, Sphingobacterium multivorum, wax The solid fungicide of shape bacillus cereus, Acinetobacter calcoaceticus and bacillus megaterium mixes with the mass ratio of 1:2:2:1:1, the most excellent Choosing, wheat bran and the mass ratio of water in the mixture of wheat bran and water are 1:1.
9. a composite biological enzyme preparation, it is characterised in that described composite biological enzyme preparation prepared by following strain and/or comprise as Lower strain: bacillus subtilis (Bacillus subtilis), Bacillus pumilus (Bacillus pumilus), candida mycoderma (Candida And Lactobacillus brevis (Lactobacillus breris) Albicans).
10. a complex micro organism fungicide, it is characterised in that described complex micro organism fungicide is prepared by following strain and/or comprises Following strain: candida tropicalis (Candida tropicalis), Sphingobacterium multivorum (Sphingobacterium multivolum), Bacillus cercus (Bacillus cereus), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus) and bacillus megaterium (Bacillus megaterium)。
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