CN106315982B - The processing system and its processing method of F- T synthesis waste water - Google Patents
The processing system and its processing method of F- T synthesis waste water Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 61
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 61
- 238000012545 processing Methods 0.000 title claims abstract description 60
- 238000003672 processing method Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 74
- 238000000909 electrodialysis Methods 0.000 claims abstract description 57
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 49
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000007524 organic acids Chemical class 0.000 claims abstract description 42
- 238000004062 sedimentation Methods 0.000 claims abstract description 28
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- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000005554 pickling Methods 0.000 claims description 20
- 238000000108 ultra-filtration Methods 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 9
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- 239000002244 precipitate Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 37
- 238000006386 neutralization reaction Methods 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
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- 235000019441 ethanol Nutrition 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 210000003850 cellular structure Anatomy 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
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- 239000000047 product Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
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- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 239000003245 coal Substances 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The present invention provides the processing systems and its processing method of a kind of F- T synthesis waste water.The processing system of the F- T synthesis waste water includes electrodialysis plant, rectifying column, anaerobic reactor, sedimentation basin and the aerobic biochemical system of sequential communication, processing system further includes iron-carbon micro-electrolysis device, the entrance of iron-carbon micro-electrolysis device and the organic acid outlet of electrodialysis plant, and the outlet of iron-carbon micro-electrolysis device is connected to the entrance of anaerobic reactor.Since the processing system further includes iron-carbon micro-electrolysis device, the entrance of iron-carbon micro-electrolysis device and the organic acid outlet of electrodialysis plant, and the outlet of iron-carbon micro-electrolysis device is connected to the entrance of anaerobic reactor, to be deacidified using electrodialysis plant to waste water before rectifying, it avoids a small amount of organic acid contained in waste water and corrosiveness is generated to rectifying device, do not have to add alkali neutralization simultaneously, avoids the larger process load for bringing a large amount of subsequent water process of scaling salt ion pair into.
Description
Technical field
The present invention relates to technical field of waste water processing, a kind of processing system in particular to F- T synthesis waste water and
Its processing method.
Background technique
Fischer-Tropsch (F-T) synthesis is under the action of catalyst, by CO and H2The technique that qualified gasoline products are made in synthesis.In
In oil product synthesis process, the water phase that F-T synthesizing section generates contains about 10% or so oxygen-containing organic compound, including alcohols, acid
Class, aldehydes, ketone etc., these organic compounds are the basic organic chemical industry products of high added value, while if this part is useless
Water can bring serious pollution without direct outlet is handled to environment.Therefore Fischer-Tropsch synthetic wastewater how is rationally handled as coal system
Critical issue urgently to be resolved during oil.
The method of processing Fischer-Tropsch synthetic wastewater is usually to pass through rectification method to carry out the oxygen-bearing organic matter in waste water at present
Recycling, however the presence of organic acid substance (predominantly acetic acid) can cause corrosion very serious to rectifier unit in waste water,
To need to be removed by pretreatment.In order to solve the above-mentioned technical problem, a kind of F- T synthesis is proposed in the prior art
The processing method of waste water, this method are then waste water is carried out biochemical treatment by adding alkali neutralization, then rectifying to extract organic matter.
In the above-mentioned methods, due to put into a large amount of NaOH and CaO, to easily entrain a large amount of fouling salt ion, subsequent water is given
Treatment for reuse brings larger process load；Also, subsequent biochemical processing generallys use conventional aeration aerobe method, due to waste water
Middle organic concentration is higher, can inhibit biodegradation, while the volumetric loading designed needed for aeration tank is higher, so this
Method treatment effeciency is low, and discharge water is extremely difficult to the discharge standard of national regulation.
Application No. is a kind of purification and recovery side of F- T synthesis water is provided in the patent application document of CN103435211A
Method, its treatment process includes adding alkali neutralization, rectifying, removing carboxylate, oxidation etc., wherein a large amount of basic species are added in pretreatment
Matter adjusts pH value, brings a large amount of fouling salt ion into, is unfavorable for subsequent waste water reclaiming processing, while using vibration reverse osmosis membrane
Technology carries out carboxylate removing, needs to provide vibration elastic force by vibrating motor for feed separation, energy consumption is larger, simultaneously because dirty
It is higher to contaminate object concentration, constantly vibration not can solve film dirt and block up problem.
Application No. is a kind of indirect liquefaction coal Ji Feituohechengshui is disclosed in the patent application document of CN104692572A
Isolation of purified processing system and method, treatment process includes filtering, oil removing, neutralization pretreatment, alcohol separation and UF membrane etc., this
Method, which equally has, brings a large amount of fouling salt ion problems into, and in addition the technique has only carried out alcohol extracting, and there is no propose organic acid
The treating method of salt.
Summary of the invention
The main purpose of the present invention is to provide the processing systems and its processing method of a kind of F- T synthesis waste water, to solve
Caustic dosage is excessive in current F- T synthesis wastewater treatment in the prior art, and lower so as to cause the water rate of recovery, water quality treatment is very
Difficult problem up to standard.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of processing system of F- T synthesis waste water
System, electrodialysis plant, rectifying column, anaerobic reactor, sedimentation basin and aerobic biochemical system including sequential communication, processing system is also
Including iron-carbon micro-electrolysis device, the entrance of iron-carbon micro-electrolysis device and the organic acid outlet of electrodialysis plant, and iron carbon is micro-
The outlet of electrolysis unit is connected to the entrance of anaerobic reactor.
Further, in anaerobic reactor anaerobic organism filler be anaerobic system effective volume 30~50%.
Further, processing system further includes oil removal filter, the outlet of oil removal filter and the entrance of electrodialysis plant
Connection.
Further, processing system further includes hyperfiltration membrane assembly, the outlet of the entrance and oil removal filter of hyperfiltration membrane assembly
Connection, the outlet of hyperfiltration membrane assembly is connected to the entrance of electrodialysis plant.
Further, the pore diameter range of ultrafiltration membrane is 50~100nm in hyperfiltration membrane assembly, and preferably ultrafiltration membrane includes organic poly-
Compound film and/or inorganic ceramic membrane.
Further, the bypass outlet of sedimentation basin is connected to the reflux inlet of anaerobic reactor, the preferably perpendicular stream of sedimentation basin
Sedimentation basin.
According to another aspect of the present invention, a kind of processing method of F- T synthesis waste water is provided, comprising the following steps: right
F- T synthesis waste water carries out electrodialysis process, obtains organic acid liquid and deacidification waste water；Rectification process is carried out to deacidification waste water, is obtained
To reaction liquid；Iron-carbon micro-electrolysis processing is carried out to organic acid liquid, obtains organic pickling agent；To reaction liquid and organic acid
Treatment fluid carries out anaerobic bio-treated and precipitates, and obtains supernatant；Aerobic biological process is carried out to supernatant, obtains wastewater treatment
Liquid.
Further, in the rectification process the step of, obtain organic gas, the rectification process the step of after, will be organic
Gas carries out separating treatment.
Further, in the step of iron-carbon micro-electrolysis is handled, current density is 10~20mA/cm2, preferred reaction time
For 2.5~3.5h, the pH value of preferably organic pickling agent is 5.7~6.0.
Further, anaerobic bio-treated, anaerobism are carried out to reaction liquid and organic pickling agent using anaerobic reactor
Anaerobic organism filler is the 30~50% of the effective volume of anaerobic reactor in reactor, and preferably the temperature of anaerobic reactor is 35
± 1 DEG C, preferred reaction time is 3~5d.
Further, in the anaerobic bio-treated the step of, Anaerobic Treatment liquid is obtained, Anaerobic Treatment liquid precipitate obtains
It precipitates mixed liquor and supernatant, and anaerobic bio-treated is carried out to partly precipitated mixed liquor, the time preferably precipitated is 1.0~
2.0h。
Further, before the electrodialysis process the step of, processing method further includes carrying out oil removing to F- T synthesis waste water
The step of processing.
Further, after the oil removal treatment the step of, processing method further includes carrying out at ultrafiltration to F- T synthesis waste water
The step of reason.
Further, in the hyperfiltration treatment the step of, F- T synthesis waste water is filtered by ultrafiltration membrane, ultrafiltration membrane
Pore diameter range is 50~100nm, and preferably ultrafiltration membrane includes organic polymer films and/or inorganic ceramic membrane.
It applies the technical scheme of the present invention, it is anti-to provide a kind of electrodialysis plant including sequential communication, rectifying column, anaerobism
The processing system for answering the F- T synthesis waste water of device, sedimentation basin and aerobic biochemical system, since the processing system further includes that iron carbon is micro-
Electrolysis unit, the entrance of iron-carbon micro-electrolysis device and the organic acid outlet of electrodialysis plant, and iron-carbon micro-electrolysis device
Outlet is connected to the entrance of anaerobic reactor, to be deacidified using electrodialysis plant to waste water before rectifying, is avoided
The a small amount of organic acid contained in waste water generates corrosiveness to rectifying device, while not having to add alkali neutralization, avoids and brings into largely
The larger process load of the subsequent water process of scaling salt ion pair；Also, it can also be using iron-carbon micro-electrolysis device to from electric osmose
The organic acid liquid of analysis apparatus carries out micro-electrolysis reaction, so that the pH value of liquid be effectively promoted, and then meets to enter and detest
The pH value requirement of oxygen system, meanwhile, the by-product Fe that iron anode is electrolysed2+It is dirty to the anaerobic organism film in subsequent anaerobic reactor
Mud has good invigoration effect, so that the more traditional anaerobic technique of anaerobic reactor has a better organic removal rate, in use
State the influent quality mark that processing system can not only make effluent quality reach integrated wastewater discharge standard level-one or reuse water process
Standard, and saved cost, easily operated, operational efficiency with higher.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
Below with reference to figure, the present invention is described in further detail.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows a kind of connection structure of the processing system of F- T synthesis waste water provided by embodiment of the present invention and shows
It is intended to.
Wherein, the above drawings include the following reference numerals:
10, electrodialysis plant；20, rectifying column；30, anaerobic reactor；40, sedimentation basin；50, aerobic biochemical system；60, iron
Carbon micro-electrolysis device；70, oil removal filter；80, hyperfiltration membrane assembly.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work
It encloses.
It should be noted that description and claims of this specification and term " first " in above-mentioned attached drawing, "
Two " etc. be to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that using in this way
Data be interchangeable under appropriate circumstances, so as to the embodiment of the present invention described herein.In addition, term " includes " and " tool
Have " and their any deformation, it is intended that cover it is non-exclusive include, for example, containing a series of steps or units
Process, method, system, product or equipment those of are not necessarily limited to be clearly listed step or unit, but may include without clear
Other step or units listing to Chu or intrinsic for these process, methods, product or equipment.
As described in background technique, caustic dosage is excessive in current F- T synthesis wastewater treatment in the prior art, from
And causing the water rate of recovery lower, water quality treatment is difficult up to standard.The present inventor studies regarding to the issue above, proposes
A kind of processing system of F- T synthesis waste water, as shown in Figure 1, including the electrodialysis plant 10 of sequential communication, rectifying column 20, detesting
Oxygen reactor 30, sedimentation basin 40 and aerobic biochemical system 50, processing system further include iron-carbon micro-electrolysis device 60, iron-carbon micro-electrolysis
The entrance of device 60 and the organic acid outlet of electrodialysis plant 10, and outlet and the anaerobic reaction of iron-carbon micro-electrolysis device 60
The entrance of device 30 is connected to.
Due to further including iron-carbon micro-electrolysis device in the processing system of above-mentioned F- T synthesis waste water, iron-carbon micro-electrolysis device
The organic acid outlet of entrance and electrodialysis plant, and the outlet of iron-carbon micro-electrolysis device and the entrance of anaerobic reactor connect
It is logical, to be deacidified using electrodialysis plant to waste water before rectifying, avoid a small amount of organic acid pair contained in waste water
Rectifying device generates corrosiveness, while not having to add alkali neutralization, avoids and brings a large amount of subsequent water process of scaling salt ion pair into
Larger process load；Also, the organic acid liquid from electrodialysis plant can also be carried out using iron-carbon micro-electrolysis device micro-
Cell reaction so that the pH value of liquid be effectively promoted, and then meets the pH value requirement into anaerobic system, meanwhile, iron
The by-product Fe that anode is electrolysed2+There is good invigoration effect to the anaerobic organism film sludge in subsequent anaerobic reactor, so that
The more traditional anaerobic technique of anaerobic reactor has better organic removal rate, can not only make to be discharged using above-mentioned processing system
Water quality reaches the influent quality standard of integrated wastewater discharge standard level-one or reuse water process, and has saved cost, has been easy to grasp
Make, operational efficiency with higher.
It is useless to F- T synthesis in order to more effectively realize in the processing system of above-mentioned F- T synthesis waste water of the invention
The anaerobic degradation of water organic pollutant, it is preferable that anaerobic organism filler is the effective volume of anaerobic system in anaerobic reactor 30
30~50%.The effective volume of above-mentioned anaerobic system refers to the practical carrying capacity (calculation formula: reactor of anaerobic reactor
Effective volume=processing flow × influent waste water organic concentration/volumetric loading).
In the processing system of above-mentioned F- T synthesis waste water of the invention, it is preferable that processing system further includes oil removing filtering
The outlet of device 70, oil removal filter 70 is connected to the entrance of electrodialysis plant 10.Using above-mentioned oil removal filter 70 to being passed through electricity
F- T synthesis waste water before electrodialysis apparatus 10 is pre-processed, to remove the oily substance in F- T synthesis waste water, due to removing
Oil strainer 70 use smart degreasing technique be by oil droplet tiny in water after the surface aggregation of material is grown up from material surface
Separation rises to water surface to realize separation, and therefore, those skilled in the art can use oleophilic drainage according to this principle
The water-oil separating filter core of material carries out water-oil separating.
In the above-mentioned processing system with oil removal filter 70, it is preferable that processing system further includes hyperfiltration membrane assembly 80,
The entrance of hyperfiltration membrane assembly 80 and the outlet of oil removal filter 70, outlet and the electrodialysis plant 10 of hyperfiltration membrane assembly 80
Entrance connection.The F- T synthesis waste water further progress for removing oily substance using 80 pairs of above-mentioned hyperfiltration membrane assembly pre-processes, with
The suspended matters such as macromolecular substances in F- T synthesis waste water are removed, having in hyperfiltration membrane assembly 80 has preferably macromolecular substances
The ultrafiltration membrane of removal ability and contamination resistance, it is preferred to use pore diameter range is the ultrafiltration membrane of 50~100nm, the material of ultrafiltration membrane
Including organic polymer films and inorganic ceramic membrane, macromolecular substances are more effectively filtered to realize.Above-mentioned ultrafiltration membrane group
The form of part 80 may include that flat, hollow fiber form, tubular type and rolling, those skilled in the art can be according to the prior arts
The form of above-mentioned hyperfiltration membrane assembly 80 is selected.
In the processing system of above-mentioned F- T synthesis waste water of the invention, it is preferable that the bypass outlet of sedimentation basin 40 with detest
The reflux inlet of oxygen reactor 30 is connected to.Above-mentioned preferred embodiment can make in sedimentation basin 40 not by above-mentioned anaerobic reaction
The part mixed liquor that device 30 is effectively treated is re-introduced into anaerobic reactor 30, therein is had to reach further to remove
The purpose of machine object, to reduce the concentration of organic matter in 40 exit supernatant of sedimentation basin.Also, compare inclined-tube sedimentation tank
And horizontal sedimentation tank, vertical sedimentation tank has many advantages, such as that occupied area is small, sedimentation effect is good, convenient for management, therefore above-mentioned precipitating
Pond 40 is preferably vertical sedimentation tank.
According to further aspect of the application, a kind of processing method of F- T synthesis waste water is provided, comprising the following steps:
Electrodialysis process is carried out to F- T synthesis waste water, obtains organic acid liquid and deacidification waste water；Rectification process is carried out to deacidification waste water,
Obtain reaction liquid；Iron-carbon micro-electrolysis processing is carried out to organic acid liquid, obtains organic pickling agent；To reaction liquid and organic
Pickling agent carries out anaerobic bio-treated and precipitates, and obtains supernatant；Aerobic biological process is carried out to supernatant, is obtained at waste water
Manage liquid.
Due to being deacidified before rectifying to waste water in the processing method of above-mentioned F- T synthesis waste water, avoid in waste water
The a small amount of organic acid contained generates corrosiveness to rectifying device, while not having to add alkali neutralization, avoids and brings a large amount of scaling salts into
The larger process load of the subsequent water process of ion pair；Also, by carrying out light electrolysis to the organic acid liquid after electrodialysis process
Reaction so that the pH value of liquid be effectively promoted, and then meets its pH value requirement for carrying out anaerobic bio-treated, meanwhile,
The by-product Fe that iron anode is electrolysed2+There is good invigoration effect to the anaerobic organism film sludge in subsequent anaerobic bio-treated,
To have better organic removal rate compared to traditional anaerobic technique, can not only be made using above-mentioned processing method
Effluent quality reaches the influent quality standard of integrated wastewater discharge standard level-one or reuse water process, and saved cost, easily
In operation, treatment effeciency with higher.
The example of the processing method of the F- T synthesis waste water provided according to the present invention is provided below in conjunction with Fig. 1
Property embodiment.However, these illustrative embodiments can be implemented by many different forms, and should not be explained
To be only limited to embodiments set forth herein.It should be understood that thesing embodiments are provided so that the application's
It is open thoroughly and complete, and the design of these illustrative embodiments is fully conveyed to those of ordinary skill in the art.
Firstly, carrying out electrodialysis process to F- T synthesis waste water, organic acid liquid and deacidification waste water are obtained.It can be by Fischer-Tropsch
Synthetic wastewater is passed through the separation chamber in electrodialysis plant 10, while deionized water is added to the concentration in electrodialysis plant 10
Room, by Na2SO4The pole room in electrodialysis plant 10 is added in solution, and opens external dc power supply, by adjusting DC power supply
The circular flow of voltage and F- T synthesis waste water realizes the removal to organic acid substances such as acetic acid in F- T synthesis waste water, and
Collect organic acid liquid.
Before the step of carrying out electrodialysis process to F- T synthesis waste water, processing method can also include to F- T synthesis
Waste water carries out the step of oil removal treatment.It can be useless to the F- T synthesis before being passed through electrodialysis plant 10 using oil removal filter 70
Water is pre-processed, to remove the oily substance in F- T synthesis waste water, the smart degreasing technique that oil removal filter 70 uses be by
Tiny oil droplet rises to water surface from material surface separation after the surface aggregation of material is grown up to realizing separation in water,
Those skilled in the art can carry out water-oil separating using the water-oil separating filter core of oleophilic drainage material according to this principle.
Further, after the above-mentioned oil removal treatment the step of, processing method can also include to F- T synthesis waste water into
The step of row hyperfiltration treatment.The F- T synthesis waste water further progress that can use 80 pairs of hyperfiltration membrane assembly removing oily substances is pre-
Processing has in hyperfiltration membrane assembly 80 to macromolecular substances to remove the suspended matters such as the macromolecular substances in F- T synthesis waste water
Ultrafiltration membrane with preferable removal ability and contamination resistance, it is preferred to use pore diameter range is the ultrafiltration membrane of 50~100nm, ultrafiltration
The material of film includes organic polymer films and inorganic ceramic membrane, to realize the filtering to macromolecular substances.
On the one hand, after completing the step of carrying out electrodialysis process to Fischer-Tropsch waste water, deacidification waste water is carried out at rectifying
Reason, obtains reaction liquid.By rectification process, to carry out organic matter recycling to above-mentioned deacidification waste water, distillation process is benefit
The reverse MULTI CONTACT of gas and liquid two phases is made by the reflux of liquid and gas with the difference of each component developability in mixture,
Under the constraint of heat-driven and phase equilibrium relationship, so that difficult volatile component is but migrated from gas phase into liquid phase, it is above-mentioned to obtain
Reaction liquid, and volatile components (light component) are constantly shifted from liquid phase into gas phase, to obtain organic gas, to realize
Separation to deacidification waste water；Also, due to isolated reaction liquid, its COD declines to a great extent, so as to use biochemical method
It is handled.Specifically, can be by deacidification waste water from 20 middle part appropriate location of rectifying column into tower, it is two that rectifying column 20, which is divided to,
Section, upper section is rectifying section, and without charging, lower section is profit reduction and reserving section containing feedboard, and condenser provides liquid-phase reflux, reboiler from tower top
Gas phase reflux is provided from tower bottom.Above-mentioned organic gas mainly includes alcohol, aldehyde and ketone etc., and organic gas can be separated further
Processing, can also be directly as fuel to obtain different component.
On the other hand, after completing the step of carrying out electrodialysis process to Fischer-Tropsch waste water, iron is carried out to organic acid liquid
Carbon micro-electrolysis processing, obtains organic pickling agent.The machine acid solution body collected in the above-mentioned electrodialysis process the step of enters iron carbon
In micro-electrolysis device 60, organic pickling agent with high ph-values is obtained, organic pickling agent meets it and carries out anaerobic organism
The pH value requirement of processing, while the by-product Fe that iron anode is electrolysed2+Have to the anaerobic organism film sludge in anaerobic bio-treated
Good invigoration effect.
In upper the step of carrying out iron-carbon micro-electrolysis processing to organic acid liquid, the work of optimization microelectrolysis processing can be passed through
Skill condition, to realize to organic acid liquid more effectively microelectrolysis processing, it is preferable that current density is 10~20mA/cm2,
Reaction time is 2.5~3.5h, and reaction liquid forms organic pickling agent in iron-carbon micro-electrolysis device 60 after pH value is promoted,
The pH value of organic pickling agent can reach 5.7~6.0, to meet its pH value requirement for carrying out anaerobic bio-treated.
After completing the step of carrying out iron-carbon micro-electrolysis processing to organic acid liquid, reaction liquid and organic acid are handled
Liquid carries out anaerobic bio-treated and precipitates, and obtains supernatant.It can be detested by adding filler in anaerobic reactor 30 with being formed
Oxygen biofilm system, to make the organic matter in above-mentioned mixed liquor be effectively removed, while the water outlet of anaerobic reactor 30
Into sedimentation basin 40, to carry out sludge reflux.
It, can be with when carrying out anaerobic bio-treated to reaction liquid and organic pickling agent using above-mentioned anaerobic reactor 30
By optimizing the process conditions of anaerobic bio-treated, to realize to mixed liquor more effectively anaerobic bio-treated.Preferably, detest
Anaerobic organism filler is the 30~50% of the effective volume of anaerobic reactor 30 in oxygen reactor 30；It is further preferable that anaerobism is anti-
The temperature for answering device 30 is 35 ± 1 DEG C, and the reaction time is 3~5d.
It is precipitated it is possible to further enter the waste water handled by anaerobic system in sedimentation basin 40, to be sunk
Shallow lake mixed liquor and supernatant, in order to realize preferably sedimentation effect, the sedimentation time is preferably 1.0~2.0h；Then, by making to sink
The bypass outlet in shallow lake pond 40 is connected to the reflux inlet of anaerobic reactor 30, not to be effectively treated by anaerobic reactor 30 to above-mentioned
Partly precipitated mixed liquor carry out anaerobic bio-treated again, to achieve the purpose that further to remove organic matter therein；Also,
Another part precipitating mixed liquor can also be made to be back to iron-carbon micro-electrolysis device 60, reflux ratio is preferably 200%, 40 bottom of sedimentation basin
The sludge in portion is discharged according to the sludge age of design, and preferably 30d discharge is primary.
After completing the step of reaction liquid and organic pickling agent are carried out anaerobic bio-treated and precipitated, to supernatant
Liquid carries out Aerobic biological process, obtains wastewater treatment liquid.It can be using aerobic biochemical system 50 to the supernatant after above-mentioned precipitating
Liquid carries out Aerobic biological process, to realize the further degradation to organic matter in supernatant, thus after making Aerobic biological process
Wastewater treatment liquid reaches discharge standard.Aerobic biochemical system 50 is that having oxygen using aerobic microbiological (including aerobic-anaerobic microbe)
It using organic pollutant present in water is that substrate carries out aerobic metabolism under the conditions of existing, by a series of biochemical reaction,
Release energy, finally settled out with the inorganic matter of low energy position step by step, reach innoxious requirement, so as to return to the nature environment or
It is further processed.Above-mentioned aerobic biochemical system 50 can be for using the techniques such as A/O method, SBR method or biofilm, art technology
Personnel can choose according to actual needs.
Further illustrate that the processing system of F- T synthesis waste water provided by the present application and Fischer-Tropsch are closed below in conjunction with embodiment
At the processing method of waste water.
Embodiment 1
Firstly, successively being pre-processed using oil removal filter and hyperfiltration membrane assembly to F- T synthesis waste water, treated
F- T synthesis waste water COD content is reduced to 30000mg/L from 50000mg/L, and all kinds of content of material are respectively as follows: methanol in waste water
1.4wt%, ethyl alcohol 2.2wt%, propyl alcohol 0.5wt%, butanol 0.2wt%, acetone 0.08wt%, acetic acid 0.5wt%；Secondly, will
Pretreated F- T synthesis waste water is added to the separation chamber of electrodialysis plant, and deionized water is added to the concentration of electric dialyzator
Room, by the Na of 0.3mol/L2SO4The pole room of solution addition electrodialysis plant.Electrodialysis DC power supply is 10V, flow 36L/h
When, other content of material are basically unchanged in waste water, and the content of organic acid is reduced to 0.05wt% from 0.5wt%, and removal rate is
90%；Third, the deacidification waste water obtained after electrodialysis process enter rectifying column and carry out organic matter extraction, feed entrance point be from upper and
Under, feeding temperature is 45 DEG C, and operating pressure is normal pressure, and reflux ratio 10, control column bottom temperature is 100~102 DEG C, tower top temperature
It is 77~79 DEG C, tower top flows out organic gas, and reaction liquid is discharged in tower bottom；The organic acid liquid obtained after electrodialysis process enters
Iron-carbon micro-electrolysis device, controls certain current density in iron-carbon micro-electrolysis device, and iron-carbon micro-electrolysis device control waterpower is stopped
Staying the time is 3h, and the size of iron-graphite electrode is 10cm × 8cm with a thickness of 5mm, and electrode plate is completely immersed in water phase, organic acid
Liquid is discharged pH value after pH value is promoted in iron-carbon micro-electrolysis device and is promoted to 5.5；4th, it is obtained by microelectrolysis processing
The reaction liquid that organic pickling agent and rectification process obtain, which is mixed into after anaerobic reactor carries out anaerobic bio-treated, to be entered
It is precipitated in vertical sedimentation tank, the filler dosage of anaerobic reactor is the 40% of anaerobic reactor effective volume, outside bio-carrier
It sees to be spherical, diameter is 5~8mm, and biologic packing material surface has apparent cellular structure, and biomembrane is mainly grown in biology and fills out
Inside the cellular structure of material, the density of bio-carrier is 3.0kg/m3, density is in 3.6kg/m after biofilm3, by anaerobic reaction
Device bottom intakes and maintains certain upflow velocity, and COD drops to 1500mg/L by 7600mg/L；Finally, the supernatant that precipitating obtains
Liquid enters aerobic biochemical system, and A sections of DO (dissolved oxygen) are not more than 0.2mg/L, and O sections of DO are 2~4mg/L, and system water outlet COD reaches
60mg/L。
Embodiment 2
Firstly, successively being pre-processed using oil removal filter and hyperfiltration membrane assembly to F- T synthesis waste water, treated
F- T synthesis waste water COD content is reduced to 38000mg/L from 60000mg/L, and all kinds of content of material are respectively as follows: methanol in waste water
1.3wt%, ethyl alcohol 2.3wt%, propyl alcohol 0.6wt%, butanol 0.1wt%, acetone 0.07wt%, acetic acid 0.6wt%；Secondly, will
Pretreated F- T synthesis waste water is added to the separation chamber of electrodialysis plant, and deionized water is added to the concentration of electric dialyzator
Room, by the Na of 0.3mol/L2SO4The pole room of solution addition electrodialysis plant.Electrodialysis DC power supply is 10V, flow 36L/h
When, other content of material are basically unchanged in waste water, and the content of organic acid is reduced to 0.05wt% from 0.6wt%, and removal rate is
91%；Third, the deacidification waste water obtained after electrodialysis process enter rectifying column and carry out organic matter extraction, feed entrance point be from upper and
Under, feeding temperature is 45 DEG C, and operating pressure is normal pressure, and reflux ratio 10, control column bottom temperature is 100~102 DEG C, tower top temperature
It is 77~79 DEG C, tower top flows out organic gas, and reaction liquid is discharged in tower bottom；The organic acid liquid obtained after electrodialysis process enters
Iron-carbon micro-electrolysis device, controls certain current density in iron-carbon micro-electrolysis device, and iron-carbon micro-electrolysis device control waterpower is stopped
Staying the time is 3h, and the size of iron-graphite electrode is 10cm × 8cm with a thickness of 5mm, and electrode plate is completely immersed in water phase, organic acid
Liquid is discharged pH value after pH value is promoted in iron-carbon micro-electrolysis device and is promoted to 5.8；4th, it is obtained by microelectrolysis processing
The reaction liquid that organic pickling agent and rectification process obtain, which is mixed into after anaerobic reactor carries out anaerobic bio-treated, to be entered
It is precipitated in vertical sedimentation tank, the filler dosage of anaerobic reactor is the 50% of anaerobic reactor effective volume, outside bio-carrier
It sees to be spherical, diameter is 5~8mm, and biologic packing material surface has apparent cellular structure, and biomembrane is mainly grown in biology and fills out
Inside the cellular structure of material, the density of bio-carrier is 3.0kg/m3, density is in 3.6kg/m after biofilm3, by anaerobic reaction
Device bottom intakes and maintains certain upflow velocity, and COD drops to 1400mg/L by 8100mg/L；Finally, the supernatant that precipitating obtains
Liquid enters aerobic biochemical system, and A sections of DO (dissolved oxygen) are not more than 0.2mg/L, and O sections of DO are 2~4mg/L, and system water outlet COD reaches
60mg/L。
Embodiment 3
Firstly, successively being pre-processed using oil removal filter and hyperfiltration membrane assembly to F- T synthesis waste water, treated
F- T synthesis waste water COD content is reduced to 32000mg/L from 56000mg/L, and all kinds of content of material are respectively as follows: methanol in waste water
1.5wt%, ethyl alcohol 2.1wt%, propyl alcohol 0.4wt%, butanol 0.3wt%, acetone 0.09wt%, acetic acid 0.4wt%；Secondly, will
Pretreated F- T synthesis waste water is added to the separation chamber of electrodialysis plant, and deionized water is added to the dense of electrodialysis plant
Contracting room, by the Na of 0.3mol/L2SO4The pole room of solution addition electrodialysis plant.Electrodialysis DC power supply is 10V, flow 36L/
When h, other content of material are basically unchanged in waste water, and the content of organic acid is reduced to 0.035wt% from 0.4wt%, and removal rate is
91%；Third, the deacidification waste water obtained after electrodialysis process enter rectifying column and carry out organic matter extraction, feed entrance point be from upper and
Under, feeding temperature is 45 DEG C, and operating pressure is normal pressure, and reflux ratio 10, control column bottom temperature is 100~102 DEG C, tower top temperature
It is 77~79 DEG C, tower top flows out organic gas, and reaction liquid is discharged in tower bottom；The organic acid liquid obtained after electrodialysis process enters
Iron-carbon micro-electrolysis device, controls certain current density in iron-carbon micro-electrolysis device, and iron-carbon micro-electrolysis device control waterpower is stopped
Staying the time is 3h, and the size of iron-graphite electrode is 10cm × 8cm with a thickness of 5mm, and electrode plate is completely immersed in water phase, organic acid
Liquid is discharged pH value after pH value is promoted in iron-carbon micro-electrolysis device and is promoted to 5.3；4th, it is obtained by microelectrolysis processing
The reaction liquid that organic pickling agent and rectification process obtain, which is mixed into after anaerobic reactor carries out anaerobic bio-treated, to be entered
It is precipitated in vertical sedimentation tank, the filler dosage of anaerobic reactor is the 50% of anaerobic reactor effective volume, outside bio-carrier
It sees to be spherical, diameter is 5~8mm, and biologic packing material surface has apparent cellular structure, and biomembrane is mainly grown in biology and fills out
Inside the cellular structure of material, the density of bio-carrier is 3.0kg/m3, density is in 3.6kg/m after biofilm3, by anaerobic reaction
Device bottom intakes and maintains certain upflow velocity, and COD drops to 1200mg/L by 7500mg/L；Finally, the supernatant that precipitating obtains
Liquid enters aerobic biochemical system, and A sections of DO (dissolved oxygen) are not more than 0.2mg/L, and O sections of DO are 2~4mg/L, and system water outlet COD reaches
55mg/L。
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
1, it is deacidified using electrodialysis plant to waste water before rectifying, avoids a small amount of organic acid contained in waste water
Corrosiveness is generated to rectifying device, while not having to add alkali neutralization, avoids and brings a large amount of subsequent water process of scaling salt ion pair into
Larger process load；
2, micro-electrolysis reaction is carried out to the organic acid liquid from electrodialysis plant using iron-carbon micro-electrolysis device, to have
The pH value of liquid is improved to effect, and then meets the pH value requirement into anaerobic system, meanwhile, the by-product that iron anode is electrolysed
Object Fe2+There is good invigoration effect to the anaerobic organism film sludge in subsequent anaerobic reactor, so that anaerobic reactor is more traditional
Anaerobic technique have better organic removal rate；
3, effluent quality can not only be made to reach integrated wastewater discharge standard level-one or recycle-water using above-mentioned processing system
The influent quality standard of processing, and saved cost, easily operated, operational efficiency with higher.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (22)
1. a kind of processing system of F- T synthesis waste water, which is characterized in that the electrodialysis plant (10) including sequential communication, rectifying
Tower (20), anaerobic reactor (30), sedimentation basin (40) and aerobic biochemical system (50), the processing system further include the micro- electricity of iron carbon
It solves device (60), the entrance of the iron-carbon micro-electrolysis device (60) and the organic acid outlet of the electrodialysis plant (10),
And the outlet of the iron-carbon micro-electrolysis device (60) is connected to the entrance of the anaerobic reactor (30).
2. processing system according to claim 1, which is characterized in that anaerobic organism filler in the anaerobic reactor (30)
It is the 30~50% of the effective volume of anaerobic system.
3. processing system according to claim 1, which is characterized in that the processing system further includes oil removal filter
(70), the outlet of the oil removal filter (70) is connected to the entrance of the electrodialysis plant (10).
4. processing system according to claim 3, which is characterized in that the processing system further includes hyperfiltration membrane assembly
(80), the outlet of the entrance of the hyperfiltration membrane assembly (80) and the oil removal filter (70), the hyperfiltration membrane assembly
(80) outlet is connected to the entrance of the electrodialysis plant (10).
5. processing system according to claim 4, which is characterized in that the aperture of ultrafiltration membrane in the hyperfiltration membrane assembly (80)
Range is 50~100nm.
6. processing system according to claim 5, which is characterized in that the ultrafiltration membrane include organic polymer films and/or
Inorganic ceramic membrane.
7. processing system according to claim 1, which is characterized in that the bypass outlet of the sedimentation basin (40) is detested with described
The reflux inlet of oxygen reactor (30) is connected to.
8. processing system according to claim 7, which is characterized in that the sedimentation basin (40) is vertical sedimentation tank.
9. a kind of processing method of F- T synthesis waste water, which comprises the following steps:
Electrodialysis process is carried out to F- T synthesis waste water, obtains organic acid liquid and deacidification waste water；
Rectification process is carried out to the deacidification waste water, obtains reaction liquid；
Iron-carbon micro-electrolysis processing is carried out to the organic acid liquid, obtains organic pickling agent；
Anaerobic bio-treated is carried out to the reaction liquid and organic pickling agent and is precipitated, supernatant is obtained；
Aerobic biological process is carried out to the supernatant, obtains wastewater treatment liquid.
10. processing method according to claim 9, which is characterized in that in the rectification process the step of, obtain organic
Gas, the rectification process the step of after, the organic gas is subjected to separating treatment.
11. processing method according to claim 9, which is characterized in that in the step of iron-carbon micro-electrolysis is handled, electricity
Current density is 10~20mA/cm2。
12. processing method according to claim 11, which is characterized in that in the step of iron-carbon micro-electrolysis is handled,
Reaction time is 2.5~3.5h.
13. processing method according to claim 11, which is characterized in that the pH value of organic pickling agent be 5.7~
6.0。
14. processing method according to claim 9, which is characterized in that using anaerobic reactor (30) to the reaction solution
Body and organic pickling agent carry out the anaerobic bio-treated, and anaerobic organism filler is institute in the anaerobic reactor (30)
State the 30~50% of the effective volume of anaerobic reactor (30).
15. processing method according to claim 14, which is characterized in that the temperature of the anaerobic reactor (30) be 35 ±
1℃。
16. processing method according to claim 14, which is characterized in that using anaerobic reactor (30) to the reaction solution
Body and organic pickling agent carry out the anaerobic bio-treated, and the reaction time is 3~5d.
17. processing method described in any one of 4 to 16 according to claim 1, which is characterized in that in the anaerobic bio-treated
The step of in, obtain Anaerobic Treatment liquid, by the Anaerobic Treatment liquid precipitate, obtain precipitating mixed liquor and the supernatant, and right
The part precipitating mixed liquor carries out the anaerobic bio-treated.
18. processing method described in any one of 4 to 16 according to claim 1, which is characterized in that the time of the precipitating is
1.0~2.0h.
19. processing method according to claim 9, which is characterized in that described before the electrodialysis process the step of
Processing method further includes the steps that carrying out oil removal treatment to the F- T synthesis waste water.
20. processing method according to claim 19, which is characterized in that described after the oil removal treatment the step of
Processing method further includes the steps that carrying out hyperfiltration treatment to the F- T synthesis waste water.
21. processing method according to claim 20, which is characterized in that, will be described in the hyperfiltration treatment the step of
F- T synthesis waste water is filtered by ultrafiltration membrane, and the pore diameter range of the ultrafiltration membrane is 50~100nm.
22. processing method according to claim 21, which is characterized in that the ultrafiltration membrane include organic polymer films and/
Or inorganic ceramic membrane.
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