CN101302067B - Innocent treatment technological process for water-based system drilling waste slurry solid-liquid separating medium - Google Patents
Innocent treatment technological process for water-based system drilling waste slurry solid-liquid separating medium Download PDFInfo
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Abstract
The present invention provides a method for a harmless treatment process of water-based system drilling waste mud solid-liquid separating medium, mainly comprising the following steps of: adjusting the pH value of the water-based system drilling waste mud solid-liquid separating medium to be a value not more than 5 by industrial acid; adding Fenton reagent into treatment fluid after pH value adjustment for oxidation treatment with the dosage of the Fenton reagent reaching between 15 and 40 ml/L, which is the content of H2O2 forming the Fenton reagent in the treatment fluid; adding neutralizing agent after oxidation reaction to adjust the pH value of the treatment fluid to be between 7 and 8 for neutralization reaction; removing filter residue via filtering after the neutralization reaction and delivering the treatment fluid into a microbial reactor; and performing a biodegradation treatment to microorganisms which are obtained from activated sludge after cultivation, domestication and filtration. After the water-based system drilling waste mud solid-liquid separating medium is treated via the method, each detection index of discharged flow does not exceed the standard, and completely achieves the comprehensive wastewater discharge standard issued by Chinese government. The method has the advantages of low treatment cost and high treatment efficiency.
Description
Technical field
The present invention relates to the drilling waste mud treatment technology, more particularly, relate to a kind of liquid phase that is used for after the water-based system drilling Separation of Solid and Liquid in Waste Mud and carry out innoxious process for treating.
Background technology
In oil and gas extraction and drilling process, can produce a large amount of drilling waste muds.The composition of waste mud is very complicated, is a kind of heterogeneous suspended substance of mainly being made up of clay, high-density weighting material, various chemical processing agent, sewage, sump oil and landwaste etc.Along with the technological development of water-based system drilling Separation of Solid and Liquid in Waste Mud is used, the innoxious subsequent disposal Study on Technology exploitation of the liquid phase after the water-based system drilling Separation of Solid and Liquid in Waste Mud more and more becomes urgent.
In recent years; improvement along with drilling technology; new low solid phase, the application of no solid phase water-based system drilling liquid; make the chemical oxygen demand (COD) (COD) of drilling waste mud or not the organic content of bio-degradable increase gradually; bring very big difficulty for the processing of drilling waste mud liquid phase, become long-term puzzlement oil-gas field environmentalist's a great problem.According to the report of China National Petroleum Corporation's environment protection communique, the drilling waste slurry solid-liquid separating medium compliance rate that enterprise of CNPC in 1998 effluxes only is 14.49%.Therefore, carry out drilling waste slurry solid-liquid separating medium harmless treatment experimental study, understand the processing mechanism of drilling waste slurry solid-liquid separating medium in depth, have very active operation significance for a processing difficult problem that solves present drilling waste slurry solid-liquid separating medium.
People have carried out many research work at the drilling waste slurry solid-liquid separating medium harmless treatment, and have obtained certain effect.At present, the processing of drilling waste slurry solid-liquid separating medium mainly contains following several treatment process:
1, chemical oxidation treatment method.This method is one of effective ways of removing pollution substance in the drilling waste slurry solid-liquid separating medium, and its basic thought is to be the harmless end product or the easy intermediate product of degraded with the pollutant oxidation in the pending parting liquid.Implement this method oxygenant commonly used clorox and hydrogen peroxide are arranged.The oxidation efficiency of clorox is very low, is aided with nickel oxide catalyst, can improve the oxidation efficiency of clorox, but the use of nickel oxide catalyst, and the one, cause the loss of nickel, introduced new pollutent chlorion again simultaneously, have certain restricted.Hydrogen peroxide is the oxygenant that a kind of feasible drilling waste slurry solid-liquid separating medium deep oxidation is handled, with Fe
2+Constitute Fenton (Fenton) reagent together.With Fenton reagent solid-liquid separating is carried out oxide treatment, Fe
2+With H
2O
2Between reaction very fast, generate the very strong hydroxyl OH radical of oxidation capacity.The oxidation capacity of hydroxyl OH radical will be higher than common chemical oxidizing agent far away, is the very strong oxygenant of a kind of oxidation capacity, can cause the many organic DeR in the solution, finally makes the fission of organic constitution generation carbochain, is oxidized to CO
2And H
2O, thus the COD value of waste water is reduced greatly.The reaction of whole system is very complicated, and its key is to pass through Fe
2+In reaction, play a part to excite and transmit, make that chain reaction can continue to carry out.With Fenton reagent solid-liquid separating is carried out oxide treatment, its insufficient place, the one, processing cost is too high, and the 2nd, can not make the whole organism in the solid-liquid separating can both obtain degraded, make solid-liquid separating obtain comprehensive harmless treatment.
2, degree of depth ozonize method.Degree of depth ozonize method is with the oxygenant of ozone as the solid-liquid separating oxide treatment, because ozone has extremely strong oxidisability, speed of response is fast, rapidly and widely some element of oxidation and organic compound.It is the strongest to two key oxidation capacities of alkenes compounds, next is amine and some carbon-to-nitrogen double bons, be alkene triple bond, carbocyclic ring, heterocyclic aromatic substance etc. once more, can reach removal organism and deodorizing, decolouring, germ-resistant purpose, and use the ozonize solid-liquid separating, can not produce mud and non-secondary pollution, therefore more and more come into one's own yet in the application aspect the solid-liquid separating harmless treatment.Its insufficient place is with as oxygenant solid-liquid separating to be carried out the existing deficiency of oxide treatment with Fenton reagent similar, the one, processing cost is too high, the 2nd, can not make the whole organic matter degradations in the solid-liquid separating, make solid-liquid separating obtain comprehensive harmless treatment.
3, microorganism treatment.Microorganism treatment is a biochemical treatment process, is bringing into play very important effect in the improvement of trade effluent, is widely used in municipal sewage treatment and Industrial Wastewater Treatment.Along with the in-depth research of microbial reaction dynamical foundation theory and the accumulation of engineering experience, biochemical processing has also obtained using widely in the improvement of poisonous, deleterious organic industrial sewage.Adopt the microbiological treatment municipal effluent and handle trade effluent, its mechanism is that microorganism in the active sludge is under the competent situation of dissolved oxygen, organism long-chain in the waste water or organic polymer can be degraded into environmentally acceptable low molecule or gas, thereby make waste water be purified processing.Because the water-based system drilling waste slurry solid-liquid separating medium composition is very complicated, up to also not finding at present the microbial strains that is specifically designed to the water-based system drilling waste slurry solid-liquid separating medium microbiological treatment, therefore, adopt single microorganism treatment effectively to handle to water-based system drilling waste slurry solid-liquid separating medium.
The existing various technology that are used for the drilling waste slurry solid-liquid separating medium harmless treatment all are based on a certain pollution feature and the water quality characteristics of drilling waste slurry solid-liquid separating medium, take single treatment process to handle.Because the heterogeneous suspended substance that drilling waste mud is made up of clay, high-density weighting material, various chemical processing agent, sewage, sump oil and landwaste etc., parting liquid after the solid-liquid separation, its composition is also very complicated, adopt single treatment process to be difficult to realize the complete harmless treatment of parting liquid usually, the method processing cost that has simultaneously is very high.Water-based system drilling waste slurry solid-liquid separating medium is implemented comprehensive treating process, be relatively more good in the industry treatment process, but up at present, it is low also not research and develop out processing cost, the processing efficiency height, the parting liquid integrated conduct method with excellent popularization and development potentiality.Researching and developing out as early as possible such parting liquid integrated conduct method, is the urgent problem of waste liquid of drilling process field.
Summary of the invention
Handle prior art at the water-based system drilling waste slurry harmless, especially the problem that the liquid phase innoxious process for treating exists after the water-based system drilling Separation of Solid and Liquid in Waste Mud, purpose of the present invention aims to provide a kind of new processing method that liquid phase after the water-based system drilling Separation of Solid and Liquid in Waste Mud is carried out comprehensive treating process, to solve water-based system drilling waste slurry solid-liquid separating medium every detection index exceeding standard of discharging current after existing treatment technology is handled, problem that can't the qualified discharge standard fundamentally solves the harm of water-based system drilling waste slurry solid-liquid separating medium to environment.
Basic thought of the present invention is, character according to water-based system drilling waste slurry solid-liquid separating medium, by various single waste liquid of drilling processing unit technology are effectively made up, found the organism in the liquid phase after a kind of aqueous based systems drilling waste mud solid-liquid separation of degrading effectively, and decolouring, deodorizing, make waste liquid of drilling can fast, economical finish the combination technological method of harmless treatment effectively, make and handle back current qualified discharge.
The to be solved above-mentioned technical problem that the present invention proposes can realize by the water-based system drilling waste slurry solid-liquid separating medium harmless treatment process with following technical scheme.
Water-based system drilling waste slurry solid-liquid separating medium harmless treatment process provided by the invention mainly comprises following processing step and parameter condition:
1, a kind of water-based system drilling waste slurry solid-liquid separating medium harmless treatment process is characterized in that mainly comprising processing step:
(1) in pending water-based system drilling waste slurry solid-liquid separating medium, adds industrial acids, the pH value of treatment solution is adjusted to is not more than 5;
(2) treatment solution that regulates of pH value adds Fenton reagent and carries out oxidizing reaction, and the add-on of Fenton reagent is for constituting the H of Fenton reagent
2O
2Content in treatment solution reaches 15～40ml/L;
(3) fully the treatment solution after the oxidizing reaction adds neutralizing agent, and the pH value of treatment solution is adjusted to 7～8, enters next process after filtration after abundant neutralization reaction;
(4) treatment solution after neutralization reaction, filtration treatment is sent into microorganism reactor, with take from active sludge through cultivate, microorganism biodegrade after the domestication, screening handles, the clear liquid current discharging after up to standard of fully degrading.
Technical scheme is handled water-based system drilling waste slurry solid-liquid separating medium in the employing, if do not reach its intended purposes, better gone out effect in order to obtain, can then carry out degree of depth oxygen with ozone to treatment solution again after treatment solution carries out oxide treatment with Fenton reagent handles, be that treatment solution carries out sending into ozone reactor after the oxide treatment with Fenton reagent, feed ozone and carry out the deep oxidation reaction, remove remaining organism in the treatment solution.Treatment solution after abundant deep oxidation reaction treatment enters the neutralization reaction operation.
In order to obtain better treatment effect, can then carry out flocculation treatment with after the treatment solution usefulness neutralizing agent neutralizing treatment with flocculation agent, make the suspended substance in the parting liquid be converted into the macrobead flco, so that filter.Flocculation agent is preferably selected polyacrylamide for use, and the add-on of polyacrylamide in treatment solution generally is not less than 0.5mg/L, is preferably 0.5～1.5mg/L.
In technique scheme, the industrial acid for adjusting pH of pending parting liquid, preferably the pH value with treatment solution is adjusted to 3.0～4.0.Said industrial acids can be sulfuric acid, nitric acid and hydrochloric acid etc., preferentially selects sulfuric acid for use.
In technique scheme, said neutralizing agent can be sodium hydroxide (NaOH), unslaked lime (CaO) etc., preferentially selects unslaked lime for use.
In technique scheme, the add-on of Fenton reagent is preferably its H that constitutes component
2O
2Content in treatment solution reaches 25～35ml/L, the H in the Fenton reagent
2O
2With Fe
2+Mol ratio be 6～9.
In the technique scheme, be used for the microorganism that biological degradation is handled, for get sewage work from active sludge, cultivate through at room temperature and to be no less than 10 days, domestication is no less than the microorganism in 2 weeks.
The contriver finds that different pH values are bigger to the organic substance influence in the Fenton reagent catalyzing oxidizing degrading treatment solution in chemical oxidation research, the pH value is crossed low all bad with too high treatment effect, and pH value treatment effect when 3-4 is reasonable.When the pH value is relatively lower, Fe
3+Difficulty is reduced to Fe
2+, can not fine performance Fe
2+The effect that excites in reaction and transmit makes that chain reaction can not continue to carry out, and has reduced H
2O
2Service efficiency, so solution C OD
CrClearance very low, solution C OD after the oxidation
CrBe worth higher; When the pH value was 3-4, Fenton reagent catalytic oxidation obtained the optimum handling effect; And along with the rising of pH value, solution C OD
CrClearance descend solution C OD after the oxidation
CrValue presents rising trend.Its reason mainly is because the pH value when higher, makes Fe in the solution easily
2+Lose catalytic capability with the form precipitation of oxyhydroxide, simultaneously H
2O
2Understand self and decompose, thereby make the H that participates in oxidation
2O
2Amount reduce, be unfavorable for the carrying out of catalyzed oxidation.So treatment solution being carried out the optimal ph of catalytic oxidation is 3-4.Treatment solution just can directly carry out Fenton reagent catalytic oxidation treatment if the liquid phase that obtains through acidifying breakdown of emulsion after-filtration then need not to regulate the pH value.
Find that also along with Fenton reagent dosage increases gradually, solution C ODcr value clearance increases gradually in contriver's research, treatment solution water outlet CODcr value after treatment reduces gradually; Work as H
2O
2Add-on be 30ml/L, FeSO
47H
2When the dosage of O was 18.6g/L, treated water outlet CODcr value was reduced to minimum value; Then along with the Fenton reagent dosage increases gradually, solution C ODcr value clearance descends gradually, and treated water outlet CODcr value raises gradually.The Fenton reagent dosage more after a little while, the OH of generation is also fewer, organism is not by abundant oxidation in the treatment solution; And the Fenton reagent dosage more for a long time, too much H
2O
2Have neither part nor lot in catalytic oxidation, increased water outlet CODcr value to a certain extent.Experimental result shows, H
2O
2Dosage be advisable 25～35ml/L preferably with 15～40ml/L.
Also have, Fenton agent treated degrading waste water, an important characteristic is exactly that speed of response is fast.In general, in the initial stage of reaction, the clearance of CODcr in time prolongation and increase, through behind the certain hour, the clearance of CODcr is near maximum value, the CODcr of water outlet reaches minimum value, then keeps stable substantially.The organic essence of Fenton agent treated is exactly that hydroxyl radical free radical and organism react, and the size of the generation speed of OH and OH and organism speed of reaction has directly determined the length of Fenton agent treated waste water required time.Therefore, need to determine the time of oxidizing reaction.Discover, increase along with oxidation time, the removal amount of CODcr reduces gradually, it is stable to tend towards stability at last, the removal amount of the 2nd hour CODcr only is half of removal amount of the 1st hour CODcr, reason is that the reduction of speed of response has produced some intermediates that are difficult to by the OH oxidation, desires to make CODcr further to be degraded, and must realize by changing reaction conditions.Therefore be not less than 1.5 hours between our negate at once.
The contriver finds that also the ozone oxidation time is an important parameter of water technology in the research of ozone deep oxidation.Under the ozone gas flow situation of having determined to feed in the treatment solution,, i.e. reaction times, just can determine the size of ozone dosage by measuring the feeding time of ozone.At the early stage of ozone oxidation reaction, COD
CrClearance very fast, the later stage is mild gradually, and along with the continuity in reaction times moves closer to horizontality, water outlet COD
CrValue tends towards stability.This is that ozone has certain selectivity to organic oxidative degradation in the water because in the whole process of ozone reaction.Feed the starting stage of ozone, what participate in reaction mainly is a little easily organism of oxidation, and these organism are become CO by ozone oxidation soon
2And H
2O.In the reaction process of back, the organism major part in the waste water is difficult for oxidized, even very difficult oxidation, and the material that promptly participates in reaction can not directly change into CO
2And H
2O, some is oxidized to other middle transformant, perhaps just macromolecular oxidation operation is become the less organism of molecular weight, and these remains COD
CrIntegral part, so oxidizing reaction speed is very slow.The oxidation time of waste water and ozone more than 2 hours the time, COD
CrRemoval effect more satisfactory.
In addition, the contriver has compared the pH value of regulating treatment solution as neutralizing agent with NaOH and CaO under study for action, lacks though find the sediment weight of regulating the back generation with NaOH, and operation is also convenient, and effluent color dilution is higher; And regulate with CaO, not only can satisfy the requirement that the pH value is regulated, and throwing out is arranged, and the effect of absorption small organic molecule particulate, all right desulfurization removing nitric is for follow-up microbiological deterioration processing creates conditions, also can save the part expense, simultaneously treatment effect also be made moderate progress.Therefore can preferentially select for use CaO as neutralization reagent.Experiment shows, the COD of waste water
CrBe worth highly more, suspension content etc. are high more, and the requirement of CaO is also big more, and the pH value of treatment solution is transferred to 7～8 from 2.4～2.8, and the dosage of CaO is generally 30～35g/L.Find that in research CaO neutralization reaction add a little polyacrylamide (concentration is 1%) again after the adding CaO neutralization reaction, the organism in the treatment solution can be converted into oarse-grained flco, and can increase filtration velocity.Find in the research, the polyacrylamide add-on after a little while, DeGrain, the too much effect of dosage is no change also, also cause waste, have only the add-on of polyacrylamide suitable, effect is remarkable, and the contriver finds by many group experiments, the polyacrylamide dosage is in 0.5～1.5mg/L scope, tangible flocculating effect is arranged, and add-on is in 1.0～1.30mg/L scope, and flocculating effect is more satisfactory.
The microorganism that the contriver is adopted in microbiological deterioration research, for from active sludge through cultivate, the microorganism of domestication, screening.The active sludge of sewage work is at municipal effluent or similar with it trade effluent, because nutrition and bacterial classification all possess, in the aeration tank, carry out continuous aeration, generally at room temperature through the active sludge flco occurring about a week, in time suitably change water and discharging excess sludge then, to supplement the nutrients and to get rid of meta-bolites.
In the culture studies of active sludge, with aerator pump (50L/min) bubbling air, adopt down to be interrupted in room temperature (5～30 ℃) and change the water mode, changed water once in per 4 hours, change to leave standstill before the water and take out supernatant liquor after about 0.5 hour, and additional tap water and nutritive ingredient.After 1 week of repetitive operation, change per 6 hours into and change water once, cultured continuously is no less than 10 days, and active sludge can be cultivated maturation.Active sludge is cultivated ripe, is embodied in after leaving standstill 0.5 hour, and the sewage in the bio-reactor clearly is divided into 3 layers, and lower floor is an active sludge, and the middle level is the active sludge flco, and the upper strata is complete transparent clear liquid.Under bio-reactor aeration state, take a morsel and leave standstill several minutes after the mixed solution, getting supernatant liquor examines under a microscope, can see a large amount of small-sized oval microorganisms, a small amount of bar rod microorganism, a small amount of large scale ellipsoidal microorganism, 3 kinds of microbial numbers are 60: 1: 1 than probably, and the microorganism total amount can be by initial 2.23 * 10
6Individual/mL rises to 5.25 * 10
6Individual/mL.
To also taming through the active sludge of cultivating (culturing micro-organisms).The purpose that active sludge is tamed is by the adaptability that domestication changes and screen microorganism, bacterium in the active sludge, to make microorganism, bacterium adapt to pending drilling waste slurry solid-liquid separating medium gradually in cultivating the domestication process.Active sludge through domestication can significantly improve organic oxidative decomposition capacity and degradation efficiency in the treatment solution.The domestication process is on the basis that active sludge is cultivated, and is interrupted and changes water and add treatment solution and the mixed solution of clear water, and wherein, the volume of treatment solution increases gradually, and with interruption change the water time gradually by changed into 8 hours in 6 hours, 12 hours.In the domestication process, constantly add a spot of treatment solution, and be not more than 200mL/ days, and increase dosage gradually, the dosage increment makes microorganism just begin to adapt to gradually new environment in culturing process for being not more than 50mL/ days.Cultivate domestication and be no less than 5 days and can observe, after bio-reactor stops aeration and leaves standstill for some time, the light tan flocks is arranged, Here it is the microorganism of wanting required for the present invention on the active sludge upper strata.And microbe population by begin to tame 5.25 * 10
6Individual/mL increases gradually, reaches maximum value 6.25 * 10 in a few days ago
6Individual/mL, then continue to increase gradually along with adding treatment solution, microbe population then begins to reduce gradually, and microbe population is gradually in being stabilized in 3.24 * 10
6Individual/mL.And in microbial inoculum, 3 kinds of microorganisms, be small-sized oval microorganism, bar rod microorganism, large scale ellipsoidal microbial numbers than changing and be stabilized in about 50: 1: 1 by initial about 60: 1: 1, promptly bar rod microorganism, large scale ellipsoidal microbial numbers increase relatively.The thalline kind of incompatibility waste liquid of drilling is eliminated in the microorganism, and remaining thalline all is the microorganism of the degraded waste liquid of drilling that can enliven.Above-mentioned phenomenon shows that microorganism has adapted to this drilling waste slurry solid-liquid separating medium, the microbial acclimation success.
The contriver finds by deep theoretical analysis in microbiological deterioration research, organism by microorganism panning after, by Metabolic activity, a part is decomposed, stable, and its physiological activity energy needed is provided; A part is transformed, synthetic new protoplasma, promptly carries out the breeding of microorganism.Microorganism interacts with pollutent in wastewater treatment, by its Metabolic activity, can make multiple biochemical reactions such as pollutent generation oxidizing reaction, reduction reaction, hydrolysis reaction, decarboxylation reaction, desamination reaction, hydroxylating, esterification.The carrying out of these reactions, can make most pollution substances, particularly in various degree conversion, decomposition or degraded take place in organism, sometimes be a kind of reactivity in pollution substance, be that multiple reaction acts on a kind of pollution substance simultaneously or acts on the different steps that pollution substance transforms sometimes.Microorganism finally is decomposed into the inorganics form to organism by multiple reaction, reaches innoxious requirement.Contain a large amount of microbic activity mud and place microorganism reactor (4.05L), the dosage of initial drilling waste slurry solid-liquid separating medium is not more than 500mL/ days, and microbe population is 3.06 * 10
6Individual/mL, increase a day dosage gradually, the dosage increment finally is stable at the solid-liquid separating dosage and is not more than 1L/ days for being not more than 50mL/ days, observes microbe population and is stable at about 2.75 * 10
6Individual/mL, i.e. microbiological deterioration treatment rate is about 1/4 of a microorganism reactor.The water outlet CODcr that handle through biological degradation this moment can be stabilized in below the 120mg/L.
The contriver is by experiment repeatedly, water-based system drilling waste slurry solid-liquid separating medium is through the preliminary oxidation of Fenton reagent, ozone deep oxidation, unslaked lime neutralization, biological degradation composite treatment process system handles, final outflow water CODcr value can drop to below the 120mg/L, and tend towards stability, and its colourity, pH value etc. all reach " integrated wastewater discharge standard " that Chinese Government formulates (GB8978-1996).Utilize the degradation treatment water outlet to support grass, breed fish, grass and fish state are good always, there are not any abnormal conditions, as seen, water-based system drilling waste slurry solid-liquid separating medium is after the comprehensive processing technique technical finesse that the present invention proposes, water outlet fully can qualified discharge, and animals and plants are had no adverse effects, and has accomplished harmless treatment fully.
The present invention is that being used for matrix is a kind of method that drilling waste slurry solid-liquid separating medium carries out comprehensive treating process, parting liquid is after harmless treatment process provided by the invention is handled, the every detection index of discharging water outlet does not all exceed standard, reached " integrated wastewater discharge standard " that Chinese Government formulates fully (GB8978-1996), fundamentally solved the harm of water-based system drilling waste slurry solid-liquid separating medium environment.Adopting the present invention is that drilling waste slurry solid-liquid separating medium is handled to matrix, and processing cost is low, and the processing efficiency height has excellent popularization and development potentiality.The waste liquid of drilling process field that openly solved of the present invention is urgently wished the problem that solves.
Embodiment
By the following examples the present invention is further described specifically.Be necessary to be pointed out that at this; following examples only are used for that the present invention is described further; can not be interpreted as limiting the scope of the invention; affiliated art skilled person makes some nonessential improvement and adjustment according to the foregoing invention content to the present invention, should still belong to protection scope of the present invention.
In following each embodiment, the consumption percentage ratio of each component is mass percent, and involved concentration is mass concentration, and involved ml/L and g/L are and add the average content of component in treatment solution.
Implement upright example 1
Pending object is the liquid phase of water-based system drilling waste mud after solid-liquid separation, and the volume of microorganism reactor is 4 liters.In pending treatment solution, add concentration and be 80% sulfuric acid, the pH value of treatment solution is adjusted to about 3; After treatment solution pH value is regulated evenly, add Fenton reagent and carry out oxidizing reaction, Fenton reagent is by H
2O
2And FeSO
47H
2O constitutes, the H in the Fenton reagent
2O
2With Fe
2+Mol ratio is 6, and the add-on of Fenton reagent constitutes component H for it
2O
2(50%) content at treatment solution is about 30ml/L, and the adding Fenton reagent oxidation reaction times was about about 2.5 hours; Treatment solution adds unslaked lime (CaO) and carries out neutralization reaction after abundant oxidizing reaction, and the add-on of unslaked lime is adjusted to about 7 for the pH value with treatment solution, and fully neutralization reaction enters down microbiological deterioration reaction process together after remove by filter filter residue.Treatment solution after the neutralization reaction filtration treatment is sent into microorganism reactor, with the active sludge of taking from Chengdu first sewage work, through under the room temperature about 10 ℃, cultivating 14 days, the microorganism biodegrade of taming 10 days is handled, through fully degraded, treat that microbial numbers is stable at about 2.75 * 10
6About individual/mL, i.e. microbiological deterioration treatment rate is about about 1 liter of every day, and the water outlet CODcr that handles through biological degradation can be stabilized in about 120mg/L.The discharging water outlet can reach " integrated wastewater discharge standard " (GB8978-1996).
Implement upright example 2
Pending object is the liquid phase of water-based system drilling waste mud after solid-liquid separation, and the volume of microorganism reactor is 4 liters.In pending treatment solution, add concentration and be 60% sulfuric acid, the pH value of treatment solution is adjusted to about 2.4.After treatment solution pH value is regulated evenly, add Fenton reagent and carry out oxidizing reaction, Fenton reagent is by H
2O
2And FeSO
47H
2O constitutes, the H in the Fenton reagent
2O
2With Fe
2+Mol ratio is 9, and the add-on of Fenton reagent constitutes component H for it
2O
2(50%) content in treatment solution is about 15ml/L, and the time that adds the reaction of Fenton reagent oxidation was about about 1.5 hours.Treatment solution after the Fenton reagent oxidation is handled then carries out degree of depth oxygen with ozone to be handled, and removes remaining organism in the treatment solution.Ozone is source of the gas with the air, by the ozone (O of system
3) producer produces, the mass concentration of ozone is about 2%, feeds in the retort the remaining organism in the treatment solution is carried out the deep oxidation reaction, and the deep oxidation reaction times was about about 2 hours.Treatment solution after the ozone deep oxidation is handled, add unslaked lime (CaO) and carry out neutralization reaction, the add-on of unslaked lime is adjusted to about 8 for the pH value with treatment solution, and fully neutralization reaction enters down microbiological deterioration reaction process together after remove by filter filter residue.Treatment solution after the neutralization reaction filtration treatment is sent into microorganism reactor, with the active sludge of taking from Chengdu first sewage work, through under the room temperature about 20 ℃, cultivating 8 days, the microorganism biodegrade of taming 12 days is handled, through fully degraded, treat that microbial numbers is stable at about 2.75 * 10
7About individual/mL, i.e. microbiological deterioration treatment rate is about about 2.0 liters of every days, and the water outlet CODcr that handles through biological degradation can be stabilized in about 110mg/L, and the discharging water outlet can reach " integrated wastewater discharge standard " (GB8978-1996).
Implement upright example 3
Pending object is the liquid phase of water-based system drilling waste mud after solid-liquid separation, and the volume of microorganism reactor is 4 liters.In pending treatment solution, add concentration and be 70% sulfuric acid, the pH value of treatment solution is adjusted to about 4.After treatment solution pH value is regulated evenly, add Fenton reagent and carry out oxidizing reaction, Fenton reagent is by H
2O
2And FeSO
47H
2O constitutes, the H in the Fenton reagent
2O
2With Fe
2+Mol ratio is 8, and the add-on of Fenton reagent constitutes component H for it
2O
2(50%) content in treatment solution is about 20ml/L, and the time that adds the reaction of Fenton reagent oxidation was about about 2.0 hours.Treatment solution after the Fenton reagent oxidation is handled then carries out degree of depth oxygen with ozone to be handled, and handles remaining organism.Ozone is source of the gas with the air, by the ozone (O of system
3) producer produces, the mass concentration of ozone is about 1%, feeds in the retort the remaining organism in the treatment solution is carried out the deep oxidation reaction, and the deep oxidation reaction times is about 3 hours.Treatment solution after the ozone deep oxidation is handled, add unslaked lime (CaO) and carry out neutralization reaction, the add-on of unslaked lime is adjusted to about 7.5 for the pH value with treatment solution, after the abundant neutralization reaction of unslaked lime, the adding mass concentration is 1% polyacrylamide flocculant, and the add-on of polyacrylamide is that the polyacrylamide amine content in the treatment solution is 1.0.Through abundant flocculation reaction after-filtration, remove filter residue and enter down microbiological deterioration reaction process together.Treatment solution after the neutralization reaction filtration treatment is sent into microorganism reactor, with the active sludge of taking from Chengdu first sewage work, through under the room temperature about 5 ℃, cultivating 21 days, the microorganism of taming 14 days is handled the treatment solution biodegrade, through fully degraded, treat that microbial numbers is stable at about 2.15 * 10
6About individual/mL, i.e. microbiological deterioration treatment rate is about about 0.8 liter of every day, and the water outlet CODcr that handles through biological degradation can be stabilized in about 110mg/L, and the discharging water outlet can reach " integrated wastewater discharge standard " (GB8978-1996).
Implement upright example 4
Processing step and the processing condition of present embodiment and embodiment 3 are basic identical, different places be that the neutralizing agent that is used for treatment solution is carried out neutralizing treatment is sodium hydroxide (NaOH).The treatment effect of present embodiment is compared with embodiment 3, and the sediment weight of generation is less, but effluent color dilution is higher.
Claims (10)
1. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process is characterized in that mainly comprising following processing step:
(1) adds industrial acids in the pending water-based system drilling waste slurry solid-liquid separating medium, treatment solution pH value is adjusted to is not more than 5;
(2) treatment solution that regulates of pH value adds Fenton reagent and carries out oxidizing reaction, and the add-on of Fenton reagent is for constituting the H of Fenton reagent
2O
2Content in treatment solution reaches 15～40ml/L;
(3) fully the treatment solution after the oxidizing reaction adds neutralizing agent, and the pH value of treatment solution is adjusted to 7～8, enters next process after filtration after the abundant neutralization reaction;
(4) treatment solution after filtering is sent into microorganism reactor, with take from active sludge through cultivate, microorganism biodegrade after the domestication, screening handles, the current discharging after up to standard of fully degrading.
2. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 1, it is characterized in that treatment solution carries out sending into ozone reactor after the oxide treatment with Fenton reagent, feed ozone and carry out the deep oxidation reaction, handle remaining organism, treat to enter the neutralization reaction operation after the abundant deep oxidation reaction treatment.
3. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 1 and 2, the adding flocculation agent carries out flocculation treatment after it is characterized in that treatment solution adding neutralizing agent neutralizing treatment, sends into microorganism reactor again and carry out the microbiological deterioration processing after flocculation, filtration treatment.
4. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 3 is characterized in that treatment solution is adjusted to 3.0～4.0 with industrial acids with the pH value.
5. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 4 is characterized in that said industrial acids is a sulfuric acid.
6. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 3 is characterized in that said neutralizing agent is a unslaked lime.
7. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 3 is characterized in that said flocculation agent selects polyacrylamide for use, and the content of polyacrylamide in treatment solution is not less than 0.5mg/L.
8. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 7 is characterized in that the add-on of polyacrylamide in treatment solution is 0.5～1.5mg/L.
9. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 3, the add-on that it is characterized in that Fenton reagent is for constituting component H
2O
2Content in treatment solution reaches 25～35ml/L, the H in the Fenton reagent
2O
2With Fe
2+Mol ratio be 6～9.
10. water-based system drilling waste slurry solid-liquid separating medium harmless treatment process according to claim 3, it is characterized in that being used for the microbial strains that biological degradation is handled, be no less than 10 days for taking from active sludge through cultivation at room temperature, tame, filter out the microbial strains at organic substance in the degraded parting liquid with water-based system drilling waste slurry solid-liquid separating medium, domestication, screening time are no less than 5 days.
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| CN103480639B (en) * | 2013-08-23 | 2017-05-17 | 中国石油化工集团公司 | Composite solidifying and stabilizing treatment method of oil-based drill cutting |
| CN107244887B (en) * | 2017-06-01 | 2020-07-21 | 中国石油化工股份有限公司 | Preparation method and application method of water-based drilling cutting adsorption filter material |
| CN109956648B (en) * | 2019-04-26 | 2021-10-22 | 西安石油大学 | Method for dewatering waste drilling mud based on Fenton oxidation instability and scale adsorption weighting coupling |
| CN112661472A (en) * | 2020-12-29 | 2021-04-16 | 鄂尔多斯市固邦环保科技有限公司 | Solidification stabilizing material for water-based drill chip landfill and solidification method of water-based drill chips |
| CN115286177A (en) * | 2022-07-26 | 2022-11-04 | 中海石油环保服务（天津）有限公司 | Water-based drilling mud recycling treatment system and method |
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| CN101190822A (en) * | 2006-11-24 | 2008-06-04 | 中国科学院生态环境研究中心 | Technique for treating sewage of high well and deep drilling well |
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