CN109384341A - Semi-coke high concentrated organic wastewater recycling treatment system and method - Google Patents
Semi-coke high concentrated organic wastewater recycling treatment system and method Download PDFInfo
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- CN109384341A CN109384341A CN201811454619.4A CN201811454619A CN109384341A CN 109384341 A CN109384341 A CN 109384341A CN 201811454619 A CN201811454619 A CN 201811454619A CN 109384341 A CN109384341 A CN 109384341A
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
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- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to a kind of semi-coke high concentrated organic wastewater recycling treatment system and methods, the system includes that sequentially connected pretreatment unit, ammonia still process mention phenol processing unit and refined filtration adsorption treatment unit, pretreatment unit is completed to pre-process to semi-coke high concentrated organic wastewater after heavy oil separation, multiphase flow separation, flocculating setting, double media filtrations and high-precision coalescence water-oil separating processing, makes coal tar in pretreated waste water, mechanical admixture processing to qualified index；Ammonia still process mention phenol processing unit conduct heat to pretreated water reuse hot steam current-carrying, counter-current extraction, make carbolic oil, water separation, realize deamination mention phenol；Waste water carries out refined filtration, depth dephenolize after refined filtration adsorption treatment unit mentions phenol to deamination, the present invention can effectively be handled semi-coke wastewater, ammonia nitrogen contained in semi-coke wastewater, phenol, oil recycling is carried out as byproduct simultaneously to recycle, the operating cost for considerably reducing environmental protecting device, it is especially pronounced to later period industrial applications effect.
Description
Technical field
The invention belongs to water-treatment technology fields, in particular to semi-coke high concentrated organic wastewater recycling treatment system and side
Method.
Background technique
Semi-coke wastewater is also known as semicoke waste water, refers to low-disintegration coal in middle low temperature distillation (about 600~800 DEG C) process and coal
Gas purification, a kind of industrial wastewater for being formed during the quenching of semi-coke steam, the waste water have " four high one is few " (high COD, high oil,
High ammonia nitrogen, high phenol, waste water yield are few) the characteristics of, wherein contain difficult to degrade, the highly toxic substance of a large amount of complicated component,
Such as ammonia, phenol, petroleum-type substance, during quenching, this partial contamination substance is largely attached in semi-coke, is seriously affected
Quality of the semi-coke as clean fuel.
Phenol contained by semi-coke wastewater, petroleum substance be it is a kind of be more toxic, the organic substance of degradability difference, exist for a long time
Aggregation can cause serious harm to human health and the ecological balance in environment, and phenol wastewater is arranged in China's water pollution thus
One of the harmful waste water solved for emphasis.On the one hand pollutant load can be minimized by administering industrial phenol wastewater, reach it
To national emission standard；On the other hand it is then to try to recycle the substances such as valuable phenol, ammonia, petroleum-type in water, realizes money
Source regeneration.
Ammonia nitrogen, phenol, petroleum substance in waste water if can purify out ammonium hydroxide, carbolic oil is made and if will become and can sell production
Product, while clear water quenching water can reach using biochemical (being not necessarily to special biochemical process at this time) by treated waste water
Or reach outlet index, if can reach industrial reuse standard (as circulating cooling make-up water reuse) by advanced treating again, this is right
For the semi-coke enterprise and coal tar hydrogenating enterprise of northern Shensi, it can not only solve enterprise and produce the environmental issue faced, while be enterprise
Industry is brought certain benefit (the carbolic oil product of ammonium hydroxide and recycling), and the water of reuse is even more more lumping weight to the North Shaanxi of serious water shortage
It wants.
Based on the above reasons, high concentrated organic wastewater progress comprehensive resource processing will be given off in semi-coke production process to compel
In the eyebrows and eyelashes, under the policy that environmental protection is increasingly kept under strict control, there is profound influence to semi-coke enterprise.Project have great social effect and
Environment protection significance, at the same recycle ammonia, carbolic oil can part offset operating cost, real meaning is also achieved using semi-coke after clear water quenching
The clean fuel of justice.
And still mature semi-coke wastewater treatment process, most semi-coke enterprises are not passed through directly both at home and abroad at present
It is used after crossing simple oil removing as coke quenching water, has seriously affected semi-coke quality.Only a few has treatment measures, processing method master
The similar coking waste water treatment process of water quality, but severe 10 times of the water-quality ratio coking wastewater of semi-coke wastewater are used for reference, waste water can give birth to
The property changed is worse, meanwhile, all there are some serious problems in various treatment process, such as a cost of investment in popularization and application at present
Height, the poisoning of operating cost height, severe reaction conditions, extractant dirty stifled or fouling, ammonia still process pipeline blockage, fluctuation of service etc. are asked
The problem of topic, this is also semi-coke wastewater process field urgent need to resolve.
Summary of the invention
In order to overcome present the problems of semi-coke wastewater treatment process, the present invention provides a kind of water quality treatments
The semi-coke high concentrated organic wastewater recycling processing method that good, stable and contamination-free generates.
Meanwhile the present invention provides a kind of places that can be realized above-mentioned semi-coke high concentrated organic wastewater recycling processing method
Reason system.
The technical scheme adopted by the invention is that:
A kind of semi-coke high concentrated organic wastewater recycling processing method comprising following processing step:
(1) it pre-processes
Semi-coke high concentrated organic wastewater is flowed through pretreatment unit to isolate after the dregs of fat and heavy coal tar further through more
Phase flow separation, flocculating setting, double media filtrations, high-precision coalescence water-oil separating processing, complete pretreatment, make pretreated useless
In water oil content be down to by 4000mg/L or more≤500mg/L, suspension content by 1000mg/L or more be down to≤50mg/L；
(2) ammonia still process proposes phenol processing
It conducts heat to pretreated water reuse hot steam current-carrying, volatilizes the ammonia being dissolved in the water and sour gas
Come, and extraction raffinate further utilizes extractant to form two phase countercurrent flow extraction, makes oily aqueous phase separation；It is oily mutually through phenol tower isolate carbolic oil and
Extractant, and water phase enters water tower buffering, obtains deamination and mentions waste water after phenol；
(3) refined filtration adsorption treatment
Waste water handles the oil content and solid suspension removed in waste water through secondary filter after step (2) deamination mentions phenol, later
It is discharged after into resin adsorption unit depth dephenolize, completes semi-coke high concentrated organic wastewater recycling treatment.
It further limits, the step (1) is specifically: semi-coke high concentrated organic wastewater is flowed through into pretreatment oil removing unit point
It separates out the dregs of fat and heavy coal tar, then the fluid flow pattern distribution isolated is adjusted, realize demulsification, then by the liquid of demulsification
Current stabilization, coalescence are carried out through separating flowing field, grease coarse separation is realized, isolates the light components in liquid and a small amount of heavy group
Point, the extraction raffinate after separation is separated through secondary filler again, makes light oil, water, heavy oil, sludge layering, and Oil Recovery, waste water further adds
Coagulant and flocculant carry out flocculating setting, remove the mechanical admixture in waste water, and treated, and sewage enters double medium filters,
Afterwards by high-precision coalescent oil-water separator, pretreatment is completed.
It further limiting, being adjusted in the step (1) to the fluid flow pattern distribution isolated realizes demulsification, then
The liquid of demulsification is subjected to current stabilization, coalescence through separating flowing field, realizes grease coarse separation, specific processing method is:
It reduces after pretreated organic wastewater is pumped into polyphase flow separator from side wall eddy flow through porous calm 122 current stabilization of plate
Liquid fluctuation, enters 123 coarse separation of coalescer, demulsification later, and the water phase droplet flowed through is agglomerated into rapidly big drop and sinks
It drops in the lower section bulk water phase of split-phase inclined plate 124, is rapidly separated water phase mutually with oil.
It further limits, the step (2) is specifically:
After step (1) pretreated water adds the lye that mass concentration is 20%, into ammonia still 21, make to be dissolved in water
In ammonia and sour gas conducted heat by 120~150 DEG C of low pressure hot steam current-carrying from top and evaporate, and tower bottom waste water
Enter in extraction tower 22 after acid adding and form counter-current extraction with extractant, is transferred to Phenol for Waste Water substance in extractant, oily phase
Enter from after overhead extraction phenol tower 24 using middle pressure steam or in press through hot steam as heat source liquid in tower heated, make steam
It is coarse powder product that kettle material is stayed after change；Water phase obtains deamination after buffering from after the extraction of 22 tower reactor of extraction tower into water tower 23 and mentions phenol
Waste water afterwards, COD≤4000mg/L of waste water after making deamination mention phenol, total phenol content≤600mg/L, oil content≤200mg/L, ammonia nitrogen
Content≤150mg/L, total sulfur content≤50mg/L.
It further limits, extractant used in step (2) is that methylisobutylketone either mass concentration is 30% tricresyl phosphate
Fourth rouge-kerosene intermixture.
It further limits, step (3) the refined filtration adsorption treatment is specifically:
Waste water handles the oil content and solid suspension removed in waste water through secondary filter after step (2) deamination mentions phenol, later
It is discharged after into resin adsorption unit depth dephenolize, and resin adsorption unit utilizes the extractant regeneration of step (2), after regeneration
In the extraction tower 22 of extractant return step (2)；Its COD≤1000mg/L of water outlet after resin adsorption unit, total phenol contain
Amount≤100mg/L, oil content≤50mg/L, ammonia-nitrogen content≤150mg/L, total sulfur content≤50mg/L.
A kind of processing system can be realized above-mentioned semi-coke high concentrated organic wastewater recycling processing method, including locate in advance
Reason unit 1, ammonia still process mention phenol processing unit 2 and refined filtration adsorption treatment unit 3, and it is single that the pretreatment unit 1, ammonia still process propose phenol processing
Member 2 and refined filtration adsorption treatment unit 3 are sequentially connected；
Pretreatment unit 1, to semi-coke high concentrated organic wastewater through heavy oil separation, multiphase flow separation, flocculating setting, double media
Pretreatment is completed after filtering and high-precision coalescence water-oil separating processing, makes coal tar, mechanical admixture in pretreated waste water
Handle qualified index；
Ammonia still process mentions phenol processing unit 2, to pretreated water reuse hot steam current-carrying heat transfer, counter-current extraction, make carbolic oil,
Water separation realizes that deamination mentions phenol；
Refined filtration adsorption treatment unit 3, waste water carries out refined filtration, depth dephenolize after mentioning phenol to deamination.
Further limit, the pretreatment unit 1 include sequentially connected pretreatment unit 11, polyphase flow separator 12,
Coagulation device 13, double medium filters 14 and a refined filtration filter 15.
Further limit, the polyphase flow separator 12 include shell 121, coalescer 123, porous calm plate 122 and
Split-phase inclined plate 124,121 one side of shell are equipped with organic wastewater entrance, and 121 other side bottom surface of shell goes out equipped with water phase
Mouthful, the porous calm plate 122 and coalescer 123 are successively set on organic wastewater entrance and water phase outlet in 121 inner cavity of shell
Between, the lower half of 121 inner cavity of shell is arranged in the split-phase inclined plate 124, and it is located at water phase and exports the other side, split-phase inclined plate 124
The distance of cavity wall is no more than the 1/3 of intracavity diameter in one lateral extent shell 121.
It further limits, the refined filtration adsorption treatment unit 3 includes sequentially connected RL- superhigh precision oil water separator 31
With resin adsorption device 32, the resin adsorption device 32 carries out adsorption bleaching, the absorption dress using macroporous resin adsorption column
It sets 32 and mentions phenol processing unit 2 with ammonia still process and connect.
Semi-coke high concentrated organic wastewater recycling treatment system of the invention and method mainly take off pretreatment, ammonia still process
Phenol, refined filtration absorbing process combine, and realize the processing of semi-coke wastewater comprehensive resource, compared with prior art, of the invention is beneficial
Effect is:
1, effectively semi-coke wastewater can be handled, while ammonia nitrogen contained in semi-coke wastewater, phenol, oil is returned
It is incorporated as recycling for byproduct, considerably reduces the operating cost of environmental protecting device, it is especially pronounced to later period industrial applications effect.
2, using multiphase flow separation, dedicated coalescence technology, waterborne oily and underwater oil efficiently separate is realized；It is set in device
Water-In-Oil, oil-in-water partial size molecule are high in the abundant liquid in future of the components such as eddy flow pre-separation, flow pattern adjustment, coalescent pack, inclined plate
Effect separation, then core component is relied on efficiently to be coalesced, it realizes that oil droplet mutually becomes continuous phase with water droplet oil dispersed, guarantees to contain in water
Oil index requirement.
3, the phenol extraction agent that mentions of the invention cooperates with regeneration with resin regeneration agent and shares, and resin utilizes extraction using a period of time
It takes agent regeneration treatment to activate, returns to extraction tower 22 later, realize that dephenolize extractant and resin regeneration agent share regeneration, make work of decolourizing
Skill proposes phenol technique perfection with ammonia still process and couples, and simplifies process, and be more advantageous to macromolecular phenols after reuse after extractant activation
The extraction of substance, and then improve extraction efficiency.
4, using dedicated tower internals technology, the efficient low-consume recycling that ammonia still process mentions phenol is realized；Ammonia still process proposes 24 internals of phenol tower and fills
Divide and consider the anti-stifled stripping section for requiring the inclined hole tower tray (BCE-IHT) for using anti-clogging good construction rectifying column, is distributed on tower tray
The inclined hole for having several rows parallel, every round mouth direction is identical, and the aperture of adjacent two rows is contrary, is staggered.Mode of operation
Under, air-flow is sprayed from inclined hole along the direction parallel with plate face, keeps the direction that gas flows on plate vertical with the direction of entrainment.
And the aperture direction that adjacent two rows are opposite, the gas that can cancel out each other is to the momentum of liquid layer, to ensure that gas-liquid contact
The stability of process and liquid layer.
5, using the micro phenol and oil in resin dedicated adsorption recovery waste water, it is biochemical that water outlet indices are greatly reduced
Degradation difficulty；By regulating and controlling resin micro channel, increases adsorbance, while being easy to resin regeneration, greatly increase resin and use the longevity
Life.Adsorbent equipment of the invention has loaded macroporous absorbent resin, uses special swelling system and pore-foaming agent in forming process
The cellular structure of resin is adjusted, to increase the adsorbance of resin, while being easy to regenerate, contamination resistance is strong, greatly
Improve the service life of resin.
6, method good treatment of water quality of the invention, good product quality, after processing COD≤3000mg/L in waste water, total phenol
Content≤350mg/L, oil content≤100mg/L, ammonia-nitrogen content≤100mg/L, total sulfur content≤50mg/L.
Detailed description of the invention
Fig. 1 is semi-coke high concentrated organic wastewater recycling processing method flow chart.
Fig. 2 is the flow chart of preprocess method in Fig. 1.
Fig. 3 is 12 structural schematic diagram of polyphase flow separator in Fig. 2.
Fig. 4 is the flow chart of ammonia still process dephenolization method in Fig. 1.
Fig. 5 is the flow chart of refined filtration adsorption method in Fig. 1.
Specific embodiment
Technical solution of the present invention is further described now in conjunction with drawings and examples, but the present invention is not limited only to
Following implementation situations.
Referring to Fig. 1, the semi-coke high concentrated organic wastewater recycling treatment system of the present embodiment includes sequentially connected pre- place
Reason unit 1, ammonia still process mention phenol processing unit 2 and refined filtration adsorption treatment unit 3；
Pretreatment unit 1, referring to fig. 2, including sequentially connected pretreatment unit 11, polyphase flow separator 12, coagulation dress
13, double medium filters 14 and a refined filtration filter 15 are set, wherein pretreatment unit 11 mainly by the dregs of fat in waste water and lacks
It measures heavy coal tar oil and carries out pre-separation.Pretreated oil-water mixture is carried out into efficient polyphase flow separator 12.Referring to figure
3, which includes shell 121, coalescer 123, porous calm plate 122 and split-phase inclined plate 124, shell 121
One side is equipped with organic wastewater entrance, and 121 other side bottom surface of shell is exported equipped with water phase, in organic wastewater entrance and water phase
Porous calm plate 122 and coalescer 123 are successively arranged in 121 inner cavity of shell between outlet, porous calmness plate 122 is by being fully welded
Mode is weldingly fixed on 121 inner cavity of shell.Reticular structure made of coalescer 123 is woven by two kinds of different materials, two kinds
Material one kind is metal material, and one kind is nonmetallic materials.Two groups of coalescers 123 abut against each other setting, and by support plate and
Porous calmness plate 122 is connected and fixed.The other side opposite with coalescer 123, which is exported, in water phase is provided with split-phase inclined plate 124, split-phase
124 height of inclined plate is lower than 121 inner cavity of shell, and the lower half position of 121 inner cavity of shell, split-phase inclined plate are fixedly connected on by being fully welded
124 height is 2/3rds of 121 cavity heights of shell.Pretreated organic wastewater is pumped into multiphase flow point from side wall eddy flow
Liquid fluctuation is reduced through porous calm 122 current stabilization of plate from after device, enters 123 coarse separation of coalescer, demulsification, the water flowed through later
Phase droplet is agglomerated into rapidly big drop and is deposited in the lower section bulk water phase of split-phase inclined plate 124, makes water phase and oily phase
It is rapidly separated.
It further illustrates, the split-phase inclined plate 124 of the present embodiment is obliquely installed, and tilt angle is 45~75 °, can be according to place
Reason amount is adjusted it, opens up at the top of split-phase inclined plate 124 jagged, forms it into segmental orifice plate, makes oily mutually in split-phase
It is flowed through at the top of split-phase inclined plate 124 under the compartmentation of inclined plate 124, and water phase is exported from the following side water phase of split-phase inclined plate 124
Outflow, into coagulation device 13.
Above-mentioned coagulation device 13 is sequentially communicated with double 14, refined filtration filters 15 of medium filter, the liquid after pre-separation
Body flows into flow pattern and adjustment device through declining liquid tube, and convection is arranged, during flow pattern arranges, as dispersed phase
Oil droplet be demulsified herein, coalesce, realize washing demulsification.Then enter separating flowing field with oil water mixture, in separating flowing field
In be provided with current stabilization and coalescing devices, stable flow field condition is provided for grease drop, realizes the efficient coarse separation of grease.?
During this, water Crude Oil is mainly removed, oil-containing in water is further decreased, forms light oil, water, heavy oil, sludge in equipment
Four layer positions, to complete oil water separation process, corrected oil is directly entered Oil Recovery tank after processing, and the dregs of fat of abjection are sent outside；
Processed waste water enters mixed flocculation plant, carries out flocculating setting in mixed flocculation plant, removes the mechanical admixture in waste water, processing
Sewage afterwards enters double medium filters 14, and by a refined filtration filter 15, coal tar in waste water and mechanical admixture are handled
To qualified index (oil-containing≤500mg/L, suspension content≤50mg/L in water), treated, and waste water enters ammonia still process mentions phenol list
Member.
Ammonia still process mentions phenol processing unit 2, referring to fig. 4, including ammonia still 21, extraction tower 22, water tower 23 and phenol tower 24, it is described
The entrance of ammonia still 21 is connected to by pipeline with the water outlet of a refined filtration filter 15, and the tower bottom water outlet of ammonia still 21 passes through
Pipeline is connected to the inlet of extraction tower 22, and mutually outlet is connected to by pipeline with phenol tower 24 the top oil of extraction tower 22, extraction tower
22 tower bottom liquid outlet is connected to by pipeline with the inlet of water tower 23, and the water phase for extracting split-phase is produced from 22 tower reactor of extraction tower
Enter water tower 23 afterwards to conduct heat using low-pressure steam, will be returned to after the vaporization of tower reactor circulation fluid heating part by 23 reboiler of water tower
In water tower 23；A large amount of water outlets of water tower 23 pass through pipeline to refined filtration adsorption treatment unit 3.
It further illustrates, 24 top gaseous phase of phenol tower is successively after 24 condenser one of phenol tower and the condensation of 24 condenser two of phenol tower
It enters in 24 return tank of phenol tower, while the fresh solvent of extraneous supplement is by entering phenol tower after flux bath and solvent submerged pump
In 24 return tanks, 24 return tank of phenol tower is divided into two-way, enters after pressurizeing all the way as phenol tower 24 back through 24 reflux pump of phenol tower
To 24 tower top of phenol tower, another way enters 22 tower bottom of extraction tower as circulation solvent after solvent circulating pump pressurizes；Phenol tower 24
Kettle material is crude phenols product, is successively entered after 24 feed exchanger of phenol tower, crude phenols reactor product cooler are cooled to 40 DEG C
Into crude phenols product pans, in the carrying device after the pressurization of crude phenols product pump.Phenol tower 24 (is pressed through using middle pressure steam in or
Hot steam) it is used as heat source, it will be returned in phenol tower 24 after the vaporization of tower reactor circulation fluid heating part by 24 reboiler of phenol tower.
It further illustrates, the stripping section of good inclined hole tower tray (BCE-IHT) the construction rectifying column of 24 anti-clogging of phenol tower, tower tray
On the parallel inclined hole of several rows is distributed with, every round mouth direction is identical, and the aperture of adjacent two rows is contrary, is staggered.Behaviour
Make under state, air-flow is sprayed from inclined hole along the direction parallel with plate face, makes the side in the direction and entrainment that gas flows on plate
To vertical, and the aperture direction that adjacent two rows are opposite, the gas that can cancel out each other is to the momentum of liquid layer, to ensure that gas
The stability of liquid contact process and liquid layer.The aperture of inclined hole tower tray 8 can be for round or U-shaped or Z-shaped structure and hole is in receipts
Type is held back, gas injection passage is formed, makes gas in injection state operation, gas orifice speed is larger, improves and tangentially washes away speed to plate face
Rate, anti-clogging is preferable, abundant further for gas-liquid contact is made, and mass transfer rate improves, and is equipped with hyoplastron, hyoplastron and tower in aperture
15 °~30 ° of angle is formed between disk disk, but is different water quality situation and water, and the inclined degree of hyoplastron can be at 15 °
It is adjusted in the range of~30 °.
It further illustrates, is filled with composite plate in extraction tower, which is made of packing layer and sieve plate layer, fills out
The top of sieve plate layer is arranged in the bed of material, and the spacing between packing layer and sieve plate layer is 0.5~0.8m and the thickness of packing layer is not small
In sieve plate layer, the advantage of packing tower plates and sieve plate has been given full play to, has kept the utilization rate of extractant higher, has further improved extraction
Take effect.
Refined filtration adsorption treatment unit 3, referring to Fig. 5, including sequentially connected RL- superhigh precision oil water separator 31 and decoloration
Device 32, the decoloration device 32 carry out adsorption bleaching using molecular sieve adsorption column, and the regenerated liquid entrance of decoloration device 32 passes through
Pipeline is connected to the inlet of extraction tower 22, and molecular sieve adsorption column is returned using the extractant after the extractant regeneration of extraction tower 22
In extraction tower 22, and the extractant after regenerating is more advantageous to the transfer of phenolic substances due to the residual of decoloration molecule, further mentions
High dephenolize rate.
With handle semi-coke wastewater (water quality are as follows: COD content has reached 43680mg/L,；Ammonia-nitrogen content (being considered with total nitrogen) reaches
1885.7mg/L is arrived；Volatile phenol content has reached 1468.4mg/L, total phenol content 10421.2mg/L；Oil content is in water
For 3327.4mg/L), using above-mentioned semi-coke high concentrated organic wastewater recycling treatment system, semi-coke high concentration organic waste is realized
Recycling of water resource processing method is specifically realized by following methods:
(1) it pre-processes
Semi-coke high concentrated organic wastewater is flowed through pretreatment unit 1 to isolate after the dregs of fat and heavy coal tar further through more
Phase flow separation, flocculating setting, double media filtrations, high-precision coalescence water-oil separating processing, complete pretreatment, make pretreated useless
In water oil content be down to by 4000mg/L or more≤500mg/L, suspension content by 1000mg/L or more be down to≤50mg/L；
Specifically: semi-coke wastewater enters pretreatment unit 11, mainly by the dregs of fat in waste water and a small amount of heavy coal tar oil into
Row pre-separation, the liquid that the oil-water mixture after separation carries out into efficient polyphase flow separator 12, after pre-separation then pass through overweight
Power cylinder carries out continuous phase water-oil separating, then flows into flow pattern and adjustment device through declining liquid tube, and convection is arranged,
During flow pattern arranges, the oil droplet as dispersed phase is demulsified herein, coalescence, realizes washing demulsification.It is then mixed with grease
It closes object and enters separating flowing field, current stabilization and coalescing devices are provided in separating flowing field, stable flow field item is provided for grease drop
Part realizes the efficient coarse separation of grease.Secondary filler separator is subsequently entered, in the process, mainly in removing water
Crude oil further decreases oil-containing in water, and light oil, water, four heavy oil, sludge layer positions are formed in equipment, to complete grease point
From process, corrected oil is directly entered Oil Recovery tank after processing, and the dregs of fat of abjection are sent outside；Processed waste water enters mixed flocculation dress
It sets, carries out flocculating setting in mixed flocculation plant, remove the mechanical admixture in waste water, treated, and sewage enters double media filtrations
Device 14, after by high-precision coalescent oil-water separator, coal tar in waste water and mechanical admixture processing (are contained to qualified index in water
Oil≤500mg/L, suspension content≤50mg/L), treated, and waste water enters ammonia still process mentions phenol unit and be further processed.
(2) ammonia still process proposes phenol processing
It conducts heat to pretreated water reuse hot steam current-carrying, volatilizes the ammonia being dissolved in the water and sour gas
Come, and extraction raffinate further utilizes extractant to form two phase countercurrent flow extraction, makes oily aqueous phase separation；It is oily mutually to isolate carbolic oil through phenol tower 24
And extractant, and water phase enters the buffering of water tower 23, obtains deamination and mentions waste water after phenol；Specifically:
Made after entering ammonia still 21 after adding alkali to be adjusted to the lye that mass concentration is 20% by pretreated waste water
The ammonia and sour gas being dissolved in the water, which are conducted heat by 120~150 DEG C of low pressure hot steam current-carrying from top, to be evaporated, acid
Property gas goes out device and goes sulfur recovery unit, and thick gas ammonia enters back into ammonium hydroxide preparation unit, and the ammonium hydroxide of content >=20% (wt%) is made
Desulfuring and denitrifying apparatus is sent to use as reducing agent.And enter in extraction tower 22 after tower bottom waste water acid adding.
After waste water is mixed with decoloration regeneration unit agent after ammonia still process, extraction tower 22 is entered, with to extractant counter-current extraction, is made
Phenol for Waste Water substance is transferred in extractant, and oil mutually enters phenol tower 24 from after overhead extraction；Water phase is adopted from 22 tower reactor of extraction tower
Enter water tower 23 after out；
Extractant can select methylisobutylketone (MIBK) either mass concentration for the mixing of 30% tbp-kerosene
Agent.
Phenol tower 24 recycles tower reactor using middle pressure steam (pressing through hot steam in or) as heat source, by 24 reboiler of phenol tower
It is returned in phenol tower 24 after the vaporization of liquid heating part.The extractant of 24 recovered overhead of phenol tower is returned into extractant agent circulation
Extraction tower 22 continues to use；Kettle material is the mixed carbolic oil of 84% (wt), can be used as and sells outside product.
Water tower 23, will be after the vaporization of tower reactor circulation fluid heating part by 23 reboiler of water tower using low-pressure steam as heat source
Back in water tower 23.The extractant of 23 recovered overhead of water tower enters in extractant agent circulation.23 kettle material of water tower is de-
Ammonia mentions waste water after phenol.
1 main technique operating condition of table
After ammonia still process mentions phenol in waste water: COD≤4000mg/L；Total phenol content≤600mg/L, oil content≤200mg/L, ammonia
Nitrogen content≤150mg/L, total sulfur content≤50mg/L.
(3) refined filtration adsorption treatment
Waste water handles the oil content and solid suspension removed in waste water through secondary filter after step (2) deamination mentions phenol, later
It is discharged after into the decoloration of molecular sieve adsorption column, completes semi-coke high concentrated organic wastewater recycling treatment.Specifically:
The waste water come out by water tower 23, after buffering, into RL- superhigh precision oil water separator 31, through oil removing, removal of impurities and
After macromolecule organic, into decoloration device 32, device is gone out after decolourizing using molecular sieve adsorption column to colourless or blush, it should
The cellular structure of resin is adjusted using special swelling system and pore-foaming agent in the forming process of molecular sieve adsorption column, to increase
Adding the adsorbance of resin, while being easy to regenerate, contamination resistance is strong, the service life of resin is greatly improved, and after decolourizing
Waste water can be used as coke quenching water use, can also pass through biochemical treatment system, after quick and easy biochemical, can reach three classes discharge mark
Quasi- outlet.And molecular sieve adsorption column mentions phenol device extractant using deamination and is regenerated, regenerated liquid returns to extraction tower 22.
Waste water quality after decoloration reaches: COD content has reached 1169.3mg/L；Ammonia-nitrogen content (being considered with total nitrogen) reaches
99.2mg/L；Volatile phenol content has reached 61.58mg/L, total phenol content 157.9mg/L；Oil content is 10.12mg/ in water
L。
Pretreatment+ammonia still process used by above-described embodiment proposes phenol+refined filtration absorbing process process, effectively by high COD, high ammonia
Nitrogen, high phenol, high oily semi-coke wastewater are handled, and COD can be down to 350 or less 3000 or less, phenol content, oil content after processing
100 or less, it is high to make the phenols rate of recovery hereinafter, dephenolization effect is good for ammonia nitrogen 100, while reducing the pressure of back segment biochemistry, useless after processing
Water is in colourless or pale red, and new technology is provided to the recycling comprehensive treatment of semi-coke wastewater, is semi-coke industry green
Cycle development lays the foundation.
Claims (10)
1. a kind of semi-coke high concentrated organic wastewater recycling processing method, it is characterised in that including following processing step:
(1) it pre-processes
Semi-coke high concentrated organic wastewater is flowed through pretreatment unit to isolate after the dregs of fat and heavy coal tar further through multiphase flow
Separation, flocculating setting, double media filtrations, high-precision coalescence water-oil separating processing, complete pretreatment, make in pretreated waste water
Oil content is down to by 4000mg/L or more≤and 500mg/L, suspension content by 1000mg/L or more be down to≤50mg/L；
(2) ammonia still process proposes phenol processing
It conducts heat to pretreated water reuse hot steam current-carrying, evaporates the ammonia being dissolved in the water and sour gas,
And extraction raffinate further utilizes extractant to form two phase countercurrent flow extraction, makes oily aqueous phase separation；It is oily mutually to isolate carbolic oil and extraction through phenol tower
Agent is taken, and water phase enters water tower buffering, obtains deamination and mentions waste water after phenol；
(3) refined filtration adsorption treatment
Waste water handles the oil content and solid suspension removed in waste water through secondary filter after step (2) deamination mentions phenol, enters later
It is discharged after resin adsorption unit depth dephenolize, completes semi-coke high concentrated organic wastewater recycling treatment.
2. semi-coke high concentrated organic wastewater recycling processing method according to claim 1, it is characterised in that: the step
(1) it is specifically: semi-coke high concentrated organic wastewater is flowed through into pretreatment oil removing unit and isolates the dregs of fat and heavy coal tar, to separation
Fluid flow pattern distribution out is adjusted, and is realized demulsification, then the liquid of demulsification is carried out current stabilization, coalescence through separating flowing field, is realized
Grease coarse separation isolates light components and a small amount of heavy component in liquid, and the extraction raffinate after separation is again through secondary filler
Separation makes light oil, water, heavy oil, sludge layering, Oil Recovery, and waste water further adds coagulant and flocculant to carry out flocculating setting,
Remove the mechanical admixture in waste water, treated sewage enters double medium filters, after by high-precision coalescent oil-water separator,
Complete pretreatment.
3. semi-coke high concentrated organic wastewater recycling processing method according to claim 2, it is characterised in that: the step
(1) being adjusted in the fluid flow pattern distribution isolated realizes demulsification, then the liquid of demulsification is carried out surely through separating flowing field
Stream, coalescence, realize grease coarse separation, specific processing method is:
Through porous calm plate (122) current stabilization liquid is reduced after pretreated organic wastewater is pumped into polyphase flow separator from side wall eddy flow
Bulk wave is dynamic, enters coalescer (123) coarse separation, demulsification later, and the water phase droplet flowed through is agglomerated into rapidly big drop and sinks
It drops in the lower section bulk water phase of split-phase inclined plate (124), is rapidly separated water phase mutually with oil.
4. semi-coke high concentrated organic wastewater recycling processing method according to claim 1, it is characterised in that: the step
(2) it is specifically:
After step (1) pretreated water adds the lye that mass concentration is 20%, into ammonia still (21), make to be dissolved in the water
Ammonia and sour gas conducted heat by 120~150 DEG C of low pressure hot steam current-carrying from top and evaporated, and tower bottom waste water adds
Enter in extraction tower (22) after acid and form counter-current extraction with extractant, is transferred to Phenol for Waste Water substance in extractant, oily phase
Enter from after overhead extraction phenol tower (24) using middle pressure steam or in press through hot steam as heat source liquid in tower heated, make water
It is coarse powder product that kettle material is stayed after vaporization；Water phase is taken off after entering water tower (23) buffering from after the extraction of extraction tower (22) tower reactor
Ammonia mentions waste water after phenol, COD≤4000mg/L of waste water after making deamination mention phenol, total phenol content≤600mg/L, oil content≤200mg/
L, ammonia-nitrogen content≤150mg/L, total sulfur content≤50mg/L.
5. semi-coke high concentrated organic wastewater recycling processing method according to claim 4, it is characterised in that: step (2)
Extractant used is that methylisobutylketone either mass concentration is 30% tbp-kerosene intermixture.
6. semi-coke high concentrated organic wastewater recycling processing method according to claim 1, it is characterised in that: the step
(3) refined filtration adsorption treatment is specifically:
Waste water handles the oil content and solid suspension removed in waste water through secondary filter after step (2) deamination mentions phenol, enters later
It is discharged after resin adsorption unit depth dephenolize, and resin adsorption unit utilizes the extractant regeneration of step (2), the extraction after regeneration
In the extraction tower (22) of agent return step (2)；Its COD≤1000mg/L of water outlet after resin adsorption unit, total phenol content
≤ 100mg/L, oil content≤50mg/L, ammonia-nitrogen content≤150mg/L, total sulfur content≤50mg/L.
7. a kind of processing system that can be realized semi-coke high concentrated organic wastewater recycling processing method described in claim 1,
Phenol processing unit (2) and refined filtration adsorption treatment unit (3) are mentioned including pretreatment unit (1), ammonia still process, it is characterised in that: described
Pretreatment unit (1), ammonia still process mention phenol processing unit (2) and refined filtration adsorption treatment unit (3) is sequentially connected；
Pretreatment unit (1), to semi-coke high concentrated organic wastewater through heavy oil separation, multiphase flow separation, flocculating setting, double medium mistakes
Pretreatment is completed after filter and high-precision coalescence water-oil separating processing, makes coal tar in pretreated waste water, at mechanical admixture
Manage qualified index；
Ammonia still process mentions phenol processing unit (2), to the heat transfer of pretreated water reuse hot steam current-carrying, counter-current extraction, makes carbolic oil, water
Separation realizes that deamination mentions phenol；
Refined filtration adsorption treatment unit (3), waste water carries out refined filtration, depth dephenolize after mentioning phenol to deamination.
8. semi-coke high concentrated organic wastewater recycling treatment system according to claim 4, which is characterized in that the pre- place
Managing unit (1) includes sequentially connected pretreatment unit (11), polyphase flow separator (12), coagulation device (13), double medium mistakes
Filter (14) and a refined filtration filter (15).
9. semi-coke high concentrated organic wastewater recycling treatment system according to claim 8, which is characterized in that the multiphase
Stream separator (12) includes shell (121), coalescer (123), porous calm plate (122) and split-phase inclined plate (124), the shell
Body (121) one side is equipped with organic wastewater entrance, and shell (121) other side bottom surface is exported equipped with water phase, the porous town
Quiet plate (122) and several coalescers (123) are successively set on organic wastewater entrance and water phase in shell (121) inner cavity and export it
Between, the lower half of split-phase inclined plate (124) setting shell (121) inner cavity is located at water phase and exports the other side.
10. semi-coke high concentrated organic wastewater recycling treatment system according to claim 4, which is characterized in that the essence
Filtering adsorption treatment unit (3) includes sequentially connected RL- superhigh precision oil water separator (31) and resin adsorption device (32), institute
It states resin adsorption device (32) and adsorption bleaching is carried out using macroporous resin adsorption column, the adsorbent equipment (32) and ammonia still process mention at phenol
Manage unit (2) connection.
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