CN104743753A - Treatment method of coal direct liquefaction wastewater - Google Patents

Treatment method of coal direct liquefaction wastewater Download PDF

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Publication number
CN104743753A
CN104743753A CN201510181838.XA CN201510181838A CN104743753A CN 104743753 A CN104743753 A CN 104743753A CN 201510181838 A CN201510181838 A CN 201510181838A CN 104743753 A CN104743753 A CN 104743753A
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China
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waste water
treatment
emulsion
oil
wastewater
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CN201510181838.XA
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Chinese (zh)
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孙延辉
葛德禹
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神华集团有限责任公司
中国神华煤制油化工有限公司
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Priority to CN201510181838.XA priority Critical patent/CN104743753A/en
Publication of CN104743753A publication Critical patent/CN104743753A/en

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Abstract

The invention discloses a treatment method of coal direct liquefaction wastewater. The treatment method comprises the following steps: performing desulfurization and ammonia nitrogen removal pretreatment on the coal direct liquefaction wastewater to obtain pretreated wastewater; performing liquid membrane method treatment on the pretreated wastewater to obtain a carbolic oil emulsion and dephenolization wastewater; and performing biological oxidation treatment on the dephenolization wastewater to obtain purified wastewater. According to the treatment method disclosed by the invention, the phenol wastewater after desulfurization and ammonia nitrogen removal is subjected to the liquid membrane method treatment, so that organic phenolic substances with toxic action on microorganisms in the wastewater can be recovered, and part of ammonia nitrogen in the wastewater can be removed; therefore, the wastewater after the biological oxidation treatment can be discharged with a standard level. By adopting the treatment method disclosed by the invention, the coal direct liquefaction wastewater can be treated in a centralized and unified manner and does not need to be treated separately, so that the treatment efficiency is greatly improved.

Description

The treatment process of DCL/Direct coal liquefaction waste water
Technical field
The present invention relates to field of waste water treatment, in particular to a kind for the treatment of process of DCL/Direct coal liquefaction waste water.
Background technology
In the process of DCL/Direct coal liquefaction, can produce containing the acid waste water compared with the high COD (ChemicalOxygen Demand, chemical oxygen demand (COD)) of hydrogen polysulfide, high ammonia nitrogen and aldehydes matter.The waste water composition that this kind of acid waste water is discharged primarily of devices such as gelatin liquefaction, coal hydrogen manufacturing, stabilized hydrogenation, hydrofining, hydrocracking, lighter hydrocarbons concentrate and sulphur recovery.Compare the waste water that the commercial runs such as refining of petroleum, petrochemical complex and other Coal Chemical Industries produce, the moiety of the waste water that each device of above-mentioned DCL/Direct coal liquefaction process is discharged is more complicated, as higher in phenol content, is up to 10000ppm; The concentration change of hydrogen sulfide and ammonia is large, and scope is between 30000ppm to 90000ppm.Therefore, intractability is larger, and, as processed not in time, more serious pollution can be caused to environment.
At present, conventional coal chemical wastewater treating technique is divided into coagulation, second-stage treatment and advanced treatment.Coagulation and pre-treatment, comprise oil removal, air supporting, precipitation, acidication, recycling etc.; Second-stage treatment is biochemical treatment mainly, usually adopts Wastewater Treated by Activated Sludge Process coal chemical industrial waste water; The common method of advanced treatment is coagulating sedimentation, advanced oxidation, subsequent biochemical process etc.But owing to there is a large amount of difficult degradation in coal chemical industrial waste water and suppressing the existence of biodegradable compound, make the biochemical treatment in second-stage treatment effectively can not remove organism in waste water.
In addition, because the water quality difference of the waste water of the various device discharges in DCL/Direct coal liquefaction process is larger, in the prior art, the waste water that each device discharges first is classified by usual needs, after being processed respectively by all kinds of waste water, then biochemical method is adopted to process further, complex treatment process, equipment is many, and operation easier is large.Also have in existing commercial process and adopt treatment by extraction DCL/Direct coal liquefaction phenolic wastewater, but its energy consumption is high, extraction agent easily remains in waste water, affects follow-up treating processes.
Although liquid-film method, in field of waste water treatment also existing application, particularly has bibliographical information also to have research in coking and gasification waste water process field.But DCL/Direct coal liquefaction waste water and traditional coal chemical industrial waste water distinguished, after particularly multiple device Waste Water Centralized is got up, phenols wherein and other unwanted components form more complicated.Therefore, still need to improve waste water treatment process of the prior art, to set up a kind for the treatment of process that effectively can process DCL/Direct coal liquefaction machinery waste water.
Summary of the invention
The present invention aims to provide a kind for the treatment of process of DCL/Direct coal liquefaction waste water, effectively can not remove the defect of the organic aldehydes matter in waste water to improve DCL/Direct coal liquefaction waste water treatment process in prior art.
To achieve these goals, according to an aspect of the present invention, provide a kind for the treatment of process of DCL/Direct coal liquefaction waste water, this treatment process comprises the following steps: carry out desulfurization, ammonia nitrogen removal pre-treatment to DCL/Direct coal liquefaction waste water, obtain pretreated waste water; Liquid-film method process is carried out to pretreated waste water, obtains carbolic oil emulsion and dephenolize waste water; And bio-oxidation process is carried out to dephenolize waste water, be purified waste water.
Further, above-mentionedly carry out liquid-film method process to pretreated waste water, the step obtaining carbolic oil emulsion and dephenolize waste water comprises: S1, for the preparation of the emulsion of emulsification pretreated waste water; S2, is scattered in emulsion in pretreated waste water, obtains mixture; And S3, liquid-film method process is carried out to mixture, obtains carbolic oil emulsion and dephenolize waste water.
Further, above-mentioned steps S1 comprises: S11, and tensio-active agent, additive, membrane solvent are mixed with oil phase according to the volume ratio of 2 ~ 6:3 ~ 10:84 ~ 95; The proportions that preferred oil phase is 3 ~ 5:5 ~ 8:87 ~ 92 by tensio-active agent, additive, membrane solvent according to volume ratio forms; S12, using massfraction be 15 ~ 20% sodium hydroxide or potassium hydroxide solution as aqueous phase, mix with oil phase, obtain oil-water mixture; And S13, by oil-water mixture with the rotating speed cutting 20 ~ 30 minutes of 2000 ~ 3000 revs/min, make stable w/o type emulsion; Wherein, the volume ratio of oil phase and aqueous phase is 1 ~ 2:1.
Further, above-mentioned tensio-active agent is selected from any one or several in Span-65, Span-80, LMS-2, L-113A and L-113B; Additive is selected from any one or two kinds of in glycerol, whiteruss; Membrane solvent is selected from any one or several in aviation kerosene, sulfonated kerosene, hydrotreated kerosene, benzene or dimethylbenzene.
Further, in above-mentioned steps S2, emulsion is scattered in pretreated waste water with continuous stirring, obtains mixture.
Further, the volumetric usage of above-mentioned emulsion is 10 ~ 20% of pretreated waste water volume.
Further, the volumetric usage of above-mentioned emulsion is 15 ~ 20% of pretreated waste water volume.
Further, in above-mentioned steps S3, mixture liquid film extraction 30 ~ 60 minutes under the stirring velocity of 80 ~ 130 revs/min, obtains carbolic oil emulsion and dephenolize waste water; Preferably liquid film extraction 40 ~ 50 minutes under the stirring velocity of 100 ~ 120 revs/min.
Further, above-mentioned liquid-film method process being carried out to mixture, after obtaining the step of carbolic oil emulsion and dephenolize waste water, also comprise and breakdown of emulsion process is carried out to carbolic oil emulsion, obtaining the step of aldehydes matter through reclaiming oil phase; Preferred breakdown of emulsion process adopts electrostatic demulsifying process.
Further, above-mentioned carrying out dephenolize waste water adopts activated sludge process or biomembrance process to process in the step of bio-oxidation process, be purified waste water.
Apply technical scheme of the present invention, by carrying out liquid-film method process to the pretreated waste water after desulfurization ammonia nitrogen removal, by in pretreated waste water, organic aldehydes matter that microorganism has a toxic action is reclaimed, also can remove the part ammonia nitrogen in pretreated waste water simultaneously, thus organic content in the waste water after subsequent bio oxide treatment is reduced greatly, reach emission standard.And adopt treatment process of the present invention, DCL/Direct coal liquefaction waste water can collection and uniform disposal, and carry out individual curing without the need to the waste water produced each coal liquification device, therefore, processing efficiency is greatly improved.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the schematic flow sheet of the treatment process of the DCL/Direct coal liquefaction waste water provided in a kind of typical embodiment according to the present invention; And
Fig. 2 shows the detailed process schematic diagram of the treatment process according to the DCL/Direct coal liquefaction waste water provided in a kind of preferred embodiment of the present invention.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
Mention as background technology part, in prior art, waste water treatment process is complicated and there is the defect low to the organic separation efficiency in waste water, in order to improve above-mentioned defect, in the typical embodiment of one provided by the invention, as shown in Figure 1, this treatment process comprises the following steps: carry out desulfurization, ammonia nitrogen removal pre-treatment to DCL/Direct coal liquefaction waste water, obtain pretreated waste water; Liquid-film method process is carried out to pretreated waste water, obtains carbolic oil emulsion and dephenolize waste water; And biochemical treatment is carried out to dephenolize waste water, be purified waste water.
Above-mentioned treatment process of the present invention, by carrying out liquid-film method process to the phenolic wastewater after desulfurization ammonia nitrogen removal, can not only reclaim organic aldehydes matter microorganism in waste water to toxic action, also can remove the part ammonia nitrogen in waste water simultaneously; Thus make the waste water after bio-oxidation process can qualified discharge.Adopt treatment process of the present invention, DCL/Direct coal liquefaction waste water can collection and uniform disposal, and without the need to individual curing, therefore, processing efficiency is greatly improved.
Liquid-film method process in above-mentioned treatment process of the present invention, in actual waste water treating processes, according to the difference of wastewater source and COD content, suitably can improve existing liquid-film method, can obtain carbolic oil emulsion and dephenolize waste water.In a kind of preferred embodiment of the present invention, above-mentionedly carry out liquid-film method process to pretreated waste water, the step obtaining carbolic oil emulsion and dephenolize waste water comprises: S1, for the preparation of the emulsion of emulsification pretreated waste water; S2, is scattered in emulsion in pretreated waste water, obtains mixture; And S3, liquid-film method process is carried out to mixture, obtains carbolic oil emulsion and dephenolize waste water.In above-mentioned liquid film extraction step, by emulsion is dispersed in pretreated waste water, emulsion is contacted with pretreated waste water relatively uniformly, and then is convenient to containing the oil phase of aldehydes matter and the layering of aqueous phase in liquid-film method treating processes, thus be convenient to being separated of follow-up carbolic oil emulsion and dephenolize waste water.
In above-mentioned liquid-film method treatment step of the present invention, emulsion can utilize the ordinary method of this area to be prepared, as long as can realize carrying out being separated of carbolic oil emulsion and dephenolize waste water to pretreated waste water of the present invention.In the another kind of preferred embodiment of the present invention, above-mentioned steps S1 comprises: S11, and tensio-active agent, additive, membrane solvent are mixed with oil phase according to the volume ratio of 2 ~ 6:3 ~ 10:84 ~ 95; S12, using the sodium hydroxide of massfraction 15 ~ 20% or potassium hydroxide solution as aqueous phase, mixes with oil phase, obtains oil-water mixture; And S13, by oil-water mixture with the rotating speed cutting 20 ~ 30 minutes of 2000 ~ 3000 revs/min, make stable w/o type emulsion; Wherein, the volume ratio of oil phase and aqueous phase is 1 ~ 2:1.
In above preferred embodiment of the present invention, by the proportion relation between each raw material of reasonable disposition oil phase and by the fixing fabric structure of oil phase in the scope of 1 ~ 2 times of aqueous phase volume, and through the shear-mixed of certain strength, the emulsion obtained is made to have good dephenolization effect to the pretreated waste water after desulfurization deamination, and the residual ammonia nitrogen of part can be removed, thus make follow-up biological treatment can remove organism in waste water more up hill and dale.In a kind of preferred embodiment of the present invention, the proportions that above-mentioned oil phase is 3 ~ 5:5 ~ 8:87 ~ 92 by tensio-active agent, additive, membrane solvent according to volume ratio forms.According to obtaining after the oil phase of this proportions and aqueous phase shear-mixed homogenizing, the separation efficiency of emulsion to the aldehydes matter in waste water and water is better, thus makes the waste water of process cleaner.
In the preparation method of above-mentioned emulsion of the present invention, the raw material of Surfactant, additive and membrane solvent there is no particular requirement, as long as enable the oil phase that obtains and aqueous phase reasonable disposition, realize being separated the carbolic oil emulsion in above-mentioned pretreated waste water and dephenolize waste water.In the present invention, tensio-active agent is selected from any one or several in Span-65, Span-80, LMS-2, L-113A and L-113B; Additive is selected from any one or two kinds of in glycerol, whiteruss; Membrane solvent is selected from any one or several in aviation kerosene, sulfonated kerosene, hydrotreated kerosene, benzene or dimethylbenzene.Above-mentioned tensio-active agent compared to existing technology in other tensio-active agent, have and form the interfacial film of higher-strength at water-oil interface, improve the stability of liquid film and the effect of separation efficiency.Because glycerol and whiteruss have the character and feature increasing viscosity, when selecting above-mentioned two kinds of additives, preparation emulsion is had to the beneficial effect of the stability of reinforcing membrane.Membrane solvent is the matrix thing forming liquid film, when adopting above-mentioned raw materials as membrane solvent, has the effect that solvability is good, operational stability is high.
In above-mentioned steps S2 of the present invention, emulsion is dispersed in pretreated waste water be in order to make emulsion relatively uniform contact with pretreated waste water, therefore, any method that emulsion can be made more uniformly to contact with pretreated waste water is all applicable to the present invention.In another preferred embodiment of the present invention, emulsion is scattered in pretreated waste water by above-mentioned steps S2 under the state of continuously stirring, obtains mixture.Under the state of continuously stirring, emulsion is scattered in pretreated waste water, make emulsion and pretreated waste water contact area and duration of contact all relative evenly.
When above-mentioned emulsion is scattered in pretreated waste water, can according to suitably adjust the volumetric usage of emulsion for the amount of pretreated waste water of process, as long as can realize in pretreated waste water containing phenol organism and aqueous phase separation.In a kind of preferred embodiment of the present invention, the volumetric usage of above-mentioned emulsion is 10 ~ 20% of pretreated waste water volume, the consumption of emulsion is controlled in the scope of 10 ~ 20% of pretreated waste water volume, the organism containing phenols in pretreated for DCL/Direct coal liquefaction waste water and aqueous phase can be effectively separated.More preferably the volumetric usage of emulsion is 15 ~ 20% of pretreated waste water volume, and emulsion and pretreated waste water volume ratio, within the scope of this, more effectively can will contain oil phase and the aqueous phase separation of aldehydes matter.
In above-mentioned treatment process of the present invention, in step S3, the mixture obtained is scattered in emulsion carries out in the process of liquid film extraction in pretreated waste water, anyly can promote that the operation of liquid film extraction effect all can be used for this step.In the present invention, preferably liquid film extraction 30 ~ 60 minutes under the stirring velocity of 80 ~ 130 revs/min, obtains carbolic oil emulsion and dephenolize waste water.Select under above-mentioned stirring velocity and by the time controling of liquid film extraction in above-mentioned time range, the aqueous phase of the oil phase of carbolic oil emulsion and dephenolize waste water can be made from the relative thoroughly layering pretreated waste water, be convenient to later separation.More preferably liquid film extraction 40 ~ 50 minutes under the stirring velocity of 100 ~ 120 revs/min, under this condition, makes the layered effect of oil phase and aqueous phase better.Certainly, before being separated of oil phase and aqueous phase, preferably after above-mentioned liquid film separation, then after leaving standstill after a while, make oil phase and aqueous phase layering more thorough.
Stating on the invention and liquid-film method process is carried out to mixture, after obtaining the step of carbolic oil emulsion and dephenolize waste water, also comprise and breakdown of emulsion process is carried out to carbolic oil emulsion, obtaining the step of aldehydes matter through reclaiming oil phase.Can be used for after above-mentioned oil phase circulation and stress reusing in liquid film extraction step.The aldehydes matter simultaneously obtained also can be recycled.
In above-mentioned breakdown of emulsion process, can high-voltage electrostatic demulsifying be selected, also can adopt chemical demulsifying process.High-voltage electrostatic demulsifying can process a large amount of emulsions; And chemical demulsifying process is relatively simple, the advantage that cost is low.The present invention is based on the consideration for the treatment of capacity, more preferably adopt high-voltage electrostatic demulsifying process.More preferably, in the step of high-voltage electrostatic demulsifying process, controlling operating voltage is 20 ~ 23V, and electric current is 8 ~ 10A, and the breakdown of emulsion time is 30 ~ 40 minutes, carries out breakdown of emulsion under this condition and the oil reservoir in carbolic oil emulsion and water layer layering can be made more obvious, more thoroughly.
In above-mentioned treatment process of the present invention, carrying out in the step of biochemical treatment to dephenolize waste water, owing to substantially not containing phenol organic matter matter in dephenolize waste water, the bio-oxidation process adopting this area to commonly use carries out processing the organism can effectively removed in waste water.In the present invention, preferably adopt suspension growth method or biomembrance process to process, be purified waste water.Adopt suspension growth method or biomembrance process to possess skills maturation, there is the beneficial effects such as effluent quality is good, investment working cost is low.
In above-mentioned treatment process of the present invention, the pre-treatment of desulfurization deamination is being carried out to DCL/Direct coal liquefaction waste water, before obtaining the step of pretreated waste water, also comprise the conventional step of DCL/Direct coal liquefaction waste water being carried out under gravity settling effect to de-oiling gas and oil removal treatment through oil gas tank.On the one hand the oily G&O in waste water is tentatively removed through this step, also prevent oil in waste water and oil gas on the other hand to the detrimentally affect of subsequent processing steps.
Further illustrate beneficial effect of the present invention below in conjunction with specific embodiments.
Embodiment 1
Pre-treatment: as shown in Figure 2, by the DCL/Direct coal liquefaction waste water containing phenol, sulphur and high ammonia nitrogen after removing oil gas and oil under the effect of oil removing gas tank at gravity settling, enter Stripping Desulfuration and ammonia nitrogen removal device carries out pre-treatment, the pretreated waste water of gained after desulfurization and ammonia nitrogen removal process, adopts the chemical oxygen demand cod that potassium bichromate determines as oxygenant crfor 22100mg/L, volatile phenol content is 0.6wt%;
Liquid-film method process: tensio-active agent L-113A, additive liquid paraffin and membrane solvent aviation kerosene are made into oil phase by the volume ratio of 5:8:87, add the sodium hydroxide solution of massfraction 15% again as aqueous phase, with 2500 revs/min of high speed shear 25 minutes, make stable w/o type emulsion; Wherein, during preparation oil phase, oil phase add-on is by volume of 1.5 times of aqueous phase;
Emulsion is scattered in continuous stirring (consumption of emulsion is by volume of 15% of pretreated waste water amount) in pretreated waste water, controls rotating speed 120 revs/min, liquid film extraction 50 minutes, stratification, lower floor aqueous phase (COD cr=1200mg/L, volatile phenol content does not detect) enter bio-oxidation treatment unit, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 40 minutes, and oil reservoir reclaims and is used for emulsion preparation facilities, and water layer processes recovery phenols further.
Bio-oxidation process: lower floor's aqueous phase enters to bio-oxidation treatment unit and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=80mg/L, volatile phenol content does not detect.
Embodiment 2
Pre-treatment: as shown in Figure 2, by the DCL/Direct coal liquefaction waste water containing phenol, sulphur and high ammonia nitrogen after removing oil gas and oil under the effect of oil removing gas tank at gravity settling, enter Stripping Desulfuration and ammonia nitrogen removal device carries out pre-treatment, the pretreated waste water of gained after desulfurization and ammonia nitrogen removal process, adopts the chemical oxygen demand cod that potassium bichromate determines as oxygenant crfor 22100mg/L, volatile phenol content is 0.6wt%;
Liquid-film method process: tensio-active agent Span-80, additive glycerol and membrane solvent sulfonated kerosene are made into oil phase by the volume ratio of 5:5:90, add the sodium hydroxide solution of massfraction 18% again as aqueous phase, with 3000 revs/min of high speed shear 25 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 2 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 18% of process wastewater flow rate) in pretreated waste water, control rotating speed 100 revs/min, continuously stirring extracts 40 minutes, stratification, lower floor aqueous phase (COD cr=1000mg/L, volatile phenol content does not detect) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 40 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out biomembrance process process, processed waste water COD cr=70mg/L, volatile phenol content does not detect.
Embodiment 3
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent Span-65, additive glycerol and membrane solvent hydrotreated kerosene are made into oil phase by the volume ratio of 3:5:92, add the sodium hydroxide solution of massfraction 15% again as aqueous phase, with 2500 revs/min of high speed shear 25 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 1.5 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 15% of process wastewater flow rate) in pretreated waste water, control rotating speed 120 revs/min, continuously stirring extracts 50 minutes, stratification, lower floor aqueous phase (COD cr=2000mg/L, volatile phenol content 0.5mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=75mg/L, volatile phenol content 0.03mg/L.
Embodiment 4
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent L-113B, additive glycerol and membrane solvent benzene are made into oil phase by the volume ratio of 4:6:90, add the potassium hydroxide solution of massfraction 18% again as aqueous phase, with 3000 revs/min of high speed shear 25 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 2 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 18% of process wastewater flow rate) in pretreated waste water, control rotating speed 100 revs/min, continuously stirring extracts 40 minutes, stratification, lower floor aqueous phase (COD cr=2200mg/L, volatile phenol content 1mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=65mg/L, volatile phenol content 0.05mg/L.
Embodiment 5
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent LMS-2, additive glycerol and membrane solvent dimethylbenzene are made into oil phase by the volume ratio of 6:3:91, add the potassium hydroxide solution of massfraction 20% again as aqueous phase, with 2000 revs/min of high speed shear 20 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 1 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 20% of process wastewater flow rate) in pretreated waste water, control rotating speed 80 revs/min, continuously stirring extracts 30 minutes, stratification, lower floor aqueous phase (COD cr=2100mg/L, volatile phenol content 0.8mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=73mg/L, volatile phenol content 0.04mg/L.
Embodiment 6
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent Span-80, additive glycerol and membrane solvent sulfonated kerosene are made into oil phase by the volume ratio of 6:4:90, add the potassium hydroxide solution of massfraction 20% again as aqueous phase, with 2000 revs/min of high speed shear 30 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 1 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 20% of process wastewater flow rate) in pretreated waste water, control rotating speed 80 revs/min, continuously stirring extracts 30 minutes, stratification, lower floor aqueous phase (COD cr=2300mg/L, volatile phenol content 1.2mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out biomembrance process process, processed waste water COD cr=68mg/L, volatile phenol content 0.06mg/L.
Embodiment 7
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent Span-80, additive glycerol and membrane solvent sulfonated kerosene are made into oil phase by the volume ratio of 2:10:88, add the potassium hydroxide solution of massfraction 20% again as aqueous phase, with 2000 revs/min of high speed shear 20 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 1 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 10% of process wastewater flow rate) in pretreated waste water, control rotating speed 130 revs/min, continuously stirring extracts 60 minutes, stratification, lower floor aqueous phase (COD cr=2400mg/L, volatile phenol content 1.5mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=86mg/L, volatile phenol content 0.06mg/L.
Embodiment 8
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent Span-80, additive glycerol and membrane solvent sulfonated kerosene are made into oil phase by the volume ratio of 2:3:95, add the potassium hydroxide solution of massfraction 20% again as aqueous phase, with 2000 revs/min of high speed shear 30 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 1 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 10% of process wastewater flow rate) in pretreated waste water, control rotating speed 130 revs/min, continuously stirring extracts 60 minutes, stratification, lower floor aqueous phase (COD cr=2500mg/L, volatile phenol content 2.0mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=95mg/L, volatile phenol content 0.07mg/L.
Embodiment 9
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent Span-80, additive glycerol and membrane solvent sulfonated kerosene are made into oil phase by the volume ratio of 5:5:90, add the potassium hydroxide solution of massfraction 15% again as aqueous phase, with 3000 revs/min of high speed shear 30 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 2.5 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 25% of process wastewater flow rate) in pretreated waste water, control rotating speed 150 revs/min, continuously stirring extracts 30 minutes, stratification, lower floor aqueous phase (COD cr=2250mg/L, volatile phenol content 0.6mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=76mg/L, volatile phenol content 0.03mg/L.
Embodiment 10 pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent Span20, additive tetrachloroethane and membrane solvent octanol are made into oil phase by the volume ratio of 6:4:90, add the potassium hydroxide solution of massfraction 20% again as aqueous phase, with 2000 revs/min of high speed shear 30 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 1 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 20% of process wastewater flow rate) in pretreated waste water, control rotating speed 80 revs/min, continuously stirring extracts 30 minutes, stratification, lower floor aqueous phase (COD cr=3050mg/L, volatile phenol content 10mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol concentration after process higher than the emission standard of GB8978-1996, COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=95mg/L, volatile phenol content 0.05mg/L.
Embodiment 11
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent Span-80, additive glycerol and membrane solvent sulfonated kerosene are made into oil phase by the volume ratio of 6:10:84, add the potassium hydroxide solution of massfraction 20% again as aqueous phase, with 2000 revs/min of high speed shear 20 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 1 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 10% of process wastewater flow rate) in pretreated waste water, control rotating speed 130 revs/min, continuously stirring extracts 60 minutes, stratification, lower floor aqueous phase (COD cr=1800mg/L, volatile phenol content 0.5mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=70mg/L, volatile phenol content 0.04mg/L.
Embodiment 12
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Liquid-film method process: tensio-active agent LMS-2, additive glycerol and membrane solvent dimethylbenzene are made into oil phase by the volume ratio of 7:11:82, add the potassium hydroxide solution of massfraction 10% again as aqueous phase, with 3500 revs/min of high speed shear 20 minutes, make stable w/o type emulsion, during preparation oil phase, oil phase add-on is by volume of 1 times of aqueous phase.Be scattered in continuous stirring by emulsion (consumption of emulsion is by volume of 20% of process wastewater flow rate) in pretreated waste water, control rotating speed 120 revs/min, continuously stirring extracts 30 minutes, stratification, lower floor aqueous phase (COD cr=2500mg/L, volatile phenol content 0.9mg/L) enter biochemical treatment apparatus, upper strata extraction phase sends into electrostatic demulsifying separation system, control operating voltage 23V, electric current 10A, breakdown of emulsion is point oil-yielding stratum and water layer after 30 minutes, and oil reservoir is back to emulsion preparation facilities, and water layer goes process further to reclaim phenols.
Bio-oxidation process: primary treated wastewater enters to biochemical treatment apparatus and carries out secondary treatment, the waste water volatile phenol after process and COD crconcentration is lower than the emission standard of GB8978-1996, and wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=98mg/L, volatile phenol content 1mg/L.
Comparative example 1
Pre-treatment: pre-treatment is carried out to DCL/Direct coal liquefaction waste water by the pre-treatment step of embodiment 1.
Bio-oxidation process: pretreated waste water is entered to biochemical treatment apparatus and carry out bio-oxidation process, wherein, biological oxidation process process adopts laboratory room small-sized aerating apparatus to carry out Wastewater Treated by Activated Sludge Process, processed waste water COD cr=6000mg/L, volatile phenol content 800mg/L.
The wastewater treatment condition of above-described embodiment 1 ~ 12 embodiment sees the following form 1:
As can be seen from the various embodiments described above, compare the method for wastewater treatment of ratio 1, the treatment process tool of DCL/Direct coal liquefaction waste water of the present invention has the following advantages: by carrying out liquid-film method process to the pretreated waste water after desulfurization deamination, by in pretreated waste water, organic aldehydes matter that microorganism has a toxic action is reclaimed, also can remove the part ammonia nitrogen in pretreated waste water simultaneously, thus organic content in the waste water after subsequent bio oxide treatment is reduced greatly, reach emission standard.And adopt treatment process of the present invention, DCL/Direct coal liquefaction waste water can collection and uniform disposal, and without the need to individual curing, therefore, processing efficiency is greatly improved.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a treatment process for DCL/Direct coal liquefaction waste water, is characterized in that, the treating method comprises following steps:
Desulfurization, ammonia nitrogen removal pre-treatment are carried out to described DCL/Direct coal liquefaction waste water, obtains pretreated waste water;
Liquid-film method process is carried out to described pretreated waste water, obtains carbolic oil emulsion and dephenolize waste water; And
Bio-oxidation process is carried out to described dephenolize waste water, is purified waste water.
2. treatment process according to claim 1, is characterized in that, carries out liquid-film method process to described pretreated waste water, and the step obtaining described carbolic oil emulsion and dephenolize waste water comprises:
S1, for the preparation of the emulsion of pretreated waste water described in emulsification;
S2, is scattered in described emulsion in described pretreated waste water, obtains mixture; And
S3, carries out liquid-film method process to described mixture, obtains carbolic oil emulsion and dephenolize waste water.
3. treatment process according to claim 2, is characterized in that, described step S1 comprises:
S11, is mixed with oil phase by tensio-active agent, additive, membrane solvent according to the volume ratio of 2 ~ 6:3 ~ 10:84 ~ 95; The proportions being preferably 3 ~ 5:5 ~ 8:87 ~ 92 by described tensio-active agent, additive, membrane solvent according to volume ratio becomes oil phase;
S12, using massfraction be 15 ~ 20% sodium hydroxide or potassium hydroxide solution as aqueous phase, mix with described oil phase, obtain oil-water mixture; And
S13, by described oil-water mixture with the rotating speed cutting 20 ~ 30 minutes of 2000 ~ 3000 revs/min, makes stable w/o type emulsion;
Wherein, the volume ratio of described oil phase and described aqueous phase is 1 ~ 2:1.
4. treatment process according to claim 3, is characterized in that, described tensio-active agent is selected from any one or several in Span-65, Span-80, LMS-2, L-113A and L-113B; Described additive is selected from any one or two kinds of in glycerol, whiteruss; Described membrane solvent is selected from any one or several in aviation kerosene, sulfonated kerosene, hydrotreated kerosene, benzene or dimethylbenzene.
5. treatment process according to claim 2, is characterized in that, in described step S2, is scattered in continuous stirring in described pretreated waste water by described emulsion, obtains described mixture.
6. the treatment process according to claim 2 or 5, is characterized in that, the volumetric usage of described emulsion is 10 ~ 20% of described pretreated waste water volume.
7. the treatment process according to claim 2 or 5, is characterized in that, the volumetric usage of described emulsion is 15 ~ 20% of described pretreated waste water volume.
8. treatment process according to claim 2, is characterized in that, in described step S3, described mixture carries out liquid-film method process 30 ~ 60 minutes under the stirring velocity of 80 ~ 130 revs/min, obtains carbolic oil emulsion and dephenolize waste water; Preferably under the stirring velocity of 100 ~ 120 revs/min, carry out liquid-film method process 40 ~ 50 minutes.
9. treatment process according to claim 1 and 2, it is characterized in that, liquid-film method process is being carried out to described mixture, after obtaining the step of described carbolic oil emulsion and dephenolize waste water, described treatment process also comprises carries out breakdown of emulsion process and reclaims oil phase obtaining the step of aldehydes matter to described carbolic oil emulsion; Preferred described breakdown of emulsion process adopts electrostatic demulsifying process.
10. treatment process according to claim 1, is characterized in that, carries out adopting activated sludge process or biomembrance process to process in the step of bio-oxidation process, purify liquid waste described in obtaining to described dephenolize waste water.
CN201510181838.XA 2015-04-16 2015-04-16 Treatment method of coal direct liquefaction wastewater CN104743753A (en)

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