CN104030486B - A kind of dephenolization treating method of residual coking ammonia water - Google Patents

A kind of dephenolization treating method of residual coking ammonia water Download PDF

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CN104030486B
CN104030486B CN201410233912.3A CN201410233912A CN104030486B CN 104030486 B CN104030486 B CN 104030486B CN 201410233912 A CN201410233912 A CN 201410233912A CN 104030486 B CN104030486 B CN 104030486B
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ammonia
tower
stripping
water
ammonium
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CN201410233912.3A
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CN104030486A (en
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韩卫荣
次新波
李欢欢
岳学军
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石家庄开发区德赛化工有限公司
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals

Abstract

The invention discloses a kind of dephenolization treating method of residual coking ammonia water.Raw gas is fixed ammonium remained ammonia and free ammonia remained ammonia after treatment respectively; Described Stagnant ammonium remained ammonia enters Stagnant ammonium phenol removal unit and carries out aftertreatment, comprises oily water separation, sedimentation oil removing and Stagnant ammonium and decomposes three operations; Described free ammonia remained ammonia enters free ammonia phenol removal unit and carries out aftertreatment, comprises sedimentation oil removing, extraction oil removing, stripping dephenolize, distillation dephenolize, extracting and dephenolizing five operations.This dephenolization treating method effectively reduces sewage quantum of output, reduces biochemical treatment pressure, and simultaneously by the phenol efficient recovery in remained ammonia, the heat between each operation is obtained for rational utilization, effectively reduces energy consumption cost; Waste water after process, COD value is very low, for the process simplifying biochemical waste water lays the first stone.

Description

A kind of dephenolization treating method of residual coking ammonia water
Technical field
The present invention relates to a kind of dephenolization treating method of residual coking ammonia water, belong to coking industry environmental protection treatment technical field.
Background technology
In process of coking, a large amount of volatile matter can be produced, i.e. raw gas.Raw gas complicated component, includes the many kinds of substances such as water vapour, tar steam, crude benzol, ammonia, hydrogen sulfide, phenol, ammonium salt, prussiate.Raw gas temperature up to 650 DEG C ~ 700 DEG C, through cooling after obtain phlegma, mainly comprise water, tar, crude benzol, ammonia, phenol etc. in phlegma; Part phlegma uses as cyclic ammonia water, and remaining phlegma is referred to as remained ammonia, carries out processing, discharging as waste water.
The traditional treatment method of remained ammonia comprises following two kinds:
1, first carry out ammonia still process process to remained ammonia, free ammonia is distilled out of, and distilled ammonia wastewater directly enters biochemical treatment workshop section, and biochemical waste water is used for wet quenching.The method does not make distilled ammonia wastewater obtain Appropriate application, and has increased the weight of biochemical load; Meanwhile, biochemical waste water is used for wet quenching, pollutent can be made to shift, cause secondary pollution to environment.
2, remained ammonia is after ammonia still process process, and distilled ammonia wastewater through biochemical treatment, multi-medium filtering, ultrafiltration, nanofiltration, reverse osmosis process, obtains strong brine successively; Again through Multi-effect Evaporation Processes, remove the salt compounds in waste water, obtain recycled water, thus realize the zero release of coking chemical waste water.The method long flow path, energy consumption are high, filtering membrane easily blocks, invest large, thus constrain it and use.
In above-mentioned two kinds for the treatment of processs, all need first to carry out ammonia still process process to remained ammonia.In ammonia still process process, in order to ensure ammonia still process effect, make ammonia overflow completely, need in remained ammonia, add alkali lye and promote to dissociate; Meanwhile, the phenol contained in remained ammonia can be converted into the form of phenolate, to continue to be dissolved in aqueous phase and to enter follow-up biochemical waste water process workshop section, not only effectively do not reclaimed but also significantly increased biochemical treatment difficulty, very easily cause waste water COD content overproof, very large pollution is caused to environment; After biochemical treatment, the organism such as phenol change into valueless mud, not only increase post-processing difficulty, and easily produce secondary pollution to environment.
Chinese patent CN103382067A discloses the novel method of a kind of deamination about residual coking ammonia water, dephenolize, denitrogenation and utilization, the method comprises ammonia still process depickling, stripping dephenolize, extracting and dephenolizing, oxide treatment, water reuse five operations, namely by carrying out the distillation of double tower economic benefits and social benefits, double tower oxidation stripping removal of ammonia and nitrogen to residual coking ammonia water, thus waste water COD is reduced.The method has that flow process is short, energy consumption is low, cost is low, the outstanding advantages of energy-conserving and environment-protective, and deamination is high except phenol efficiency, can realize Zero-discharge coked wastewater, and coking production is economized on water significantly.But, the method problem that still unresolved remained ammonia treatment capacity is large, postprocessing working procedures is complicated.
By analysis, include solid ammonium-salt and free ammonia in remained ammonia simultaneously.Raw gas after cooling enters gas-liquid separator, the solid ammonium-salt carried secretly in raw gas and about 60% coal tar be condensed, gained phlegma, mainly containing solid ammonium-salt, is called Stagnant ammonium remained ammonia; The residual gas of effusion enters coal gas primary cooler and cools further, main containing free ammonia and phenol in gained phlegma, is called free ammonia remained ammonia.When ammonia still process process, free ammonia can directly be distilled out of, and solid ammonium-salt needs first to be converted into free ammonia with alkali effect, then is distilled out of.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of dephenolization treating method of residual coking ammonia water, this treatment process improves the rate of recovery of phenol, achieves the reduction of discharging of coking chemical waste water, reduces environmental protection treatment cost, add Business Economic Benefit simultaneously, less investment, cost be low, energy-conserving and environment-protective.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A dephenolization treating method for residual coking ammonia water, raw gas sprays cooling, gas-liquid separator separates through cyclic ammonia water, and be fixed ammonium remained ammonia and residual gas, residual gas continues to enter coal gas primary cooler and cools, and obtains free ammonia remained ammonia; Described Stagnant ammonium remained ammonia enters Stagnant ammonium phenol removal unit and carries out aftertreatment, and described free ammonia remained ammonia enters free ammonia phenol removal unit and carries out aftertreatment.
Further improvement of the present invention is: described Stagnant ammonium phenol removal unit comprises oily water separation, sedimentation oil removing and Stagnant ammonium and decomposes three operations, and treatment facility comprises mechanical settling tank, 2# adsorption and sedimentation oil eliminator and Stagnant ammonium decomposition tower;
Described free ammonia phenol removal unit comprises sedimentation oil removing, extraction oil removing, stripping dephenolize, distillation dephenolize, extracting and dephenolizing five operations, and treatment facility comprises 1# adsorption and sedimentation oil eliminator, extracting and dephenolizing tower, pressurization stripping tower and atmospheric distillation tower.
The detailed process of described Stagnant ammonium remained ammonia aftertreatment is:
Operation one, oily water separation
First Stagnant ammonium remained ammonia enters mechanical settling tank and carries out oily water separation, the tar be mingled with in removing Stagnant ammonium remained ammonia;
Operation two, sedimentation oil removing
The Stagnant ammonium remained ammonia obtained by operation one enters 2# adsorption and sedimentation oil eliminator, removes residu(al)tar further;
Operation three, Stagnant ammonium decompose
Stagnant ammonium remained ammonia after oil removing is admitted to Stagnant ammonium decomposition tower top; In Stagnant ammonium decomposition tower, Stagnant ammonium remained ammonia and alkali lye react, and Stagnant ammonium decomposes and is converted into ammonia steam, drain into other workshop sections by Stagnant ammonium decomposition tower tower top, deliver to other workshop sections utilize by the ammonium solution waste water of discharging at the bottom of Stagnant ammonium decomposition tower tower.
The detailed process of described free ammonia remained ammonia aftertreatment is:
Operation A, sedimentation oil removing
Free ammonia remained ammonia enters 1# adsorption and sedimentation oil eliminator, by the tar be mingled with in adsorption and sedimentation removing free ammonia remained ammonia;
Process B, extraction oil removing
Free ammonia remained ammonia from operation A is admitted to the middle part of extracting and dephenolizing tower, and the extraction agent passed into bottom extracts, further removing residu(al)tar and a small amount of phenol;
Operation C, stripping dephenolize
Free ammonia remained ammonia from process B is admitted to pressurization stripping tower top, and the pressurized vapor passed into pressurization stripping tower bottom interacts, and completes the deamination dephenolize of free ammonia remained ammonia; Stripped vapor is by the side take-off of the stripping tower that pressurizes;
Step D, distillation dephenolize
Stripped vapor is condensed into stripping phlegma through cooling, is admitted in the middle part of atmospheric distillation tower; By heating, the free ammonia in stripping phlegma and part water are converted into gas, are discharged by air distillation column overhead, and phenol is stayed in aqueous phase becomes dense phenol water, discharged by the bottom of atmospheric distillation tower;
Operation E, extracting and dephenolizing
Dense phenol water from step D is again returned to extracting and dephenolizing tower, is entered by the opening for feed on extracting and dephenolizing tower top, phenol in dense phenol water and tar extraction are in extraction agent, and dephenolize water enters pressurization stripping tower by dephenolize remained ammonia groove and carries out circulation phenol removal.
Further improvement of the present invention is: the isolated tar of described operation one enters oil product storage tank by tar output channel and stores; Be provided with the cyclic ammonia water output channel be connected with coke oven collecting main in the middle and upper part of mechanical settling tank, the part in Stagnant ammonium remained ammonia directly cools to raw gas as cyclic ammonia water;
In described operation three, first Stagnant ammonium remained ammonia carries out heat exchange with the dense phenol water of atmospheric distillation tower extraction, then is admitted to the top of Stagnant ammonium decomposition tower; Alkali lye is injected by the middle part of Stagnant ammonium decomposition tower; The heat of Stagnant ammonium decomposition tower tower reactor is from ammonium solution waste water and stripped vapor.
Further improvement of the present invention is: in described operation C, free ammonia remained ammonia is divided into two portions by pipeline, a part is directly admitted to the top of pressurization stripping tower, and another part first carries out heat exchange with treatment of wastewater from stripping and then is admitted to the middle part of the stripping tower that pressurizes; The stripping waste gas of being overflowed by pressurization stripper top goes to other workshop sections by pipeline and carries out deep processing; After the oil removing of 3# adsorption and sedimentation oil eliminator, two portions are divided into by the treatment of wastewater from stripping of discharging at the bottom of pressurization stripping tower tower, part treatment of wastewater from stripping is delivered to gas washing workshop section through 1# water stripping output channel, and another part treatment of wastewater from stripping is delivered to biochemical treatment workshop section through 2# water stripping output channel;
In described step D, the gas mixture of being discharged by air distillation column overhead enters ammoniacal liquor light oil separator tank and carries out oily water separation after sub-zero treatment, obtains strong aqua and contains benzene light oil; Gained strong aqua sends into post-treatment workshop section by strong aqua output channel; Gained containing benzene light oil be transported to crude benzol groove, mix with crude benzol after use as extraction agent;
In described process B and operation E, the extraction agent from crude benzol groove is entered by the bottom of extracting and dephenolizing tower, by the overhead extraction of extracting and dephenolizing tower, then store through entering oil product storage tank containing phenol crude benzol output channel.
Further improvement of the present invention is: the tar obtained in described 1# adsorption and sedimentation oil eliminator, 2# adsorption and sedimentation oil eliminator is separated by reentering gas-liquid separator after line-blending; After the ammonium solution vapor mixing that the stripping waste gas of pressurization stripper top effusion and Stagnant ammonium decomposition tower top are discharged, carry out deep processing through row of conduits to yellow prussiate of potash production workshop section.
Owing to have employed technique scheme, the technical progress acquired by the present invention is:
The invention provides a kind of dephenolization treating method of residual coking ammonia water, the method effectively reduces sewage quantum of output, reduces biochemical treatment pressure, simultaneously by the phenol efficient recovery in remained ammonia, the heat between each operation is obtained for rational utilization, effectively reduces energy consumption cost; Waste water after process, COD value is very low, for the process simplifying biochemical waste water lays the first stone.This treatment process has that less investment, cost are low, the advantage of energy-conserving and environment-protective, can realize the reduction of discharging of coking chemical waste water, even zero release, and increase the rate of recovery of by-product phenol, while reduction environmental protection treatment cost, increase Business Economic Benefit.
Stagnant ammonium remained ammonia and free ammonia remained ammonia are carried out aftertreatment by the present invention respectively.Stagnant ammonium remained ammonia not containing phenol decomposes the process of three operations through oily water separation, sedimentation oil removing and Stagnant ammonium, residue waste water is delivered to biochemical treatment workshop section and carried out biochemical treatment.Phenol is mainly present in free ammonia remained ammonia, through the process of sedimentation oil removing, extraction oil removing, stripping dephenolize, distillation dephenolize, extracting and dephenolizing four operations, phenol can be separated completely with tar from aqueous phase, collected phenol and tar can be recycled by deep processing.
In the present invention, at the bottom of the tower that pressurization stripping tower produces, wastewater discharge sum accounts for about 80% of total wastewater discharge, and the COD value of this part waste water is less than 1000mg/L, and ammonia nitrogen value is less than 100mg/L; At the bottom of Stagnant ammonium decomposition tower tower, wastewater discharge accounts for about 20% of total wastewater discharge.In whole phenol removal process, recycling is completed to the waste water that major part produces, such as, utilizes strong aqua to prepare anhydrous ammonia, utilize dense phenol Water Sproading phenol etc., therefore, greatly reduce the wastewater flow rate needing to carry out biochemical treatment, alleviate biochemical treatment load; And in treating processes, most of organism is separated completely from aqueous phase, because this simplify the step of biochemical treatment, finally reach the zero release of residual coking ammonia water.
Adopt dephenolization treating method of the present invention, the phenol being originally converted into mud is obtained and again reclaims, often produce 10,000 tons of coke and just can reclaim phenol about 2.63 tons more, can sell as byproduct, substantially increase the economic benefit of coal chemical enterprise.
In extracting and dephenolizing tower, the present invention adopts the crude benzol of recovery and extracts as extraction agent Pyrogentisinic Acid containing benzene light oil.Compared with conventional extraction agent tar, the present invention not only has better extracting and separating effect, and also achieves crude benzol and the recycling containing benzene light oil products, reduces the environmental protection pressure of coal chemical enterprise.
In the last handling process of free ammonia remained ammonia, first twice oil removing is carried out by 1# adsorption and sedimentation oil eliminator and extraction oil removing dephenolize tower, by the most tar in free ammonia remained ammonia and the removing of a small amount of phenol, thus in follow-up stripping phenol removal process, stripping intractability reduces greatly, and decreasing the cleaning frequency of pressurization stripping tower, suitability for industrialized is produced more.
Accompanying drawing explanation
Fig. 1 is the schema of the dephenolize novel process of residual coking ammonia water of the present invention;
Wherein, 1, gas-liquid separator, 2, coal gas primary cooler, 3, mechanical settling tank, 4, coal gas primary cooler condensate trap, 5, 1# adsorption and sedimentation oil eliminator, 6, 2# adsorption and sedimentation oil eliminator, 7, extracting and dephenolizing tower, 8, dephenolize remained ammonia groove, 9, free ammonia wastewater trough, 10, pressurization stripping tower, 11, Stagnant ammonium decomposition tower well heater, 12, stripping condensation liquid bath, 13, atmospheric distillation tower, 14, dense phenol tank, 15, Stagnant ammonium decomposition tower, 16, Stagnant ammonium remained ammonia groove, 17, 3# adsorption and sedimentation oil eliminator, 18, raw gas input channel, 19, tar output channel, 20, cyclic ammonia water output channel, 21, stripping retort gas output channel, 22, 1# water stripping output channel, 23, 2# water stripping output channel, 24, Stagnant ammonium decomposition tower waste water output channel, 25, strong aqua output channel, 26, containing phenol crude benzol groove, 27, containing phenol crude benzol output channel, 28, crude benzol groove, 29, crude benzol input channel, 30, ammoniacal liquor light oil separator tank.
Black arrow in figure represents the trend of free ammonia remained ammonia, and double-headed arrow represents the trend of Stagnant ammonium remained ammonia.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further details:
A dephenolization treating method for residual coking ammonia water, as shown in Figure 1, raw gas sprays through cyclic ammonia water and lowers the temperature in effuser, enters gas-liquid separator 1, be separated to obtain Stagnant ammonium remained ammonia and residual gas by raw gas input channel 18.Stagnant ammonium remained ammonia enters Stagnant ammonium phenol removal unit and carries out aftertreatment, residual gas continues to enter coal gas primary cooler 2 and cools, obtain free ammonia remained ammonia, free ammonia remained ammonia is temporary in coal gas primary cooler condensate trap 4, then enter free ammonia phenol removal unit and carry out aftertreatment.
(1) aftertreatment of Stagnant ammonium remained ammonia
Stagnant ammonium phenol removal unit decomposes three operations by oily water separation, sedimentation oil removing and Stagnant ammonium and forms, and main treatment facility comprises the mechanical settling tank 3,2# adsorption and sedimentation oil eliminator 6 and the Stagnant ammonium decomposition tower 15 that connect successively.
The detailed process of described Stagnant ammonium remained ammonia aftertreatment is:
Operation one, oily water separation
First Stagnant ammonium remained ammonia enters mechanical settling tank 3, and the difference according to profit density completes oily water separation, thus reaches the object of the tar in removing Stagnant ammonium remained ammonia; Isolated tar enters oil product storage tank through tar output channel 19 and stores;
Be provided with liquid outlet in mechanical settling tank 3 middle and upper part, this liquid outlet is connected with coke oven collecting main by cyclic ammonia water output channel 20, and the part in Stagnant ammonium remained ammonia directly cools to raw gas as cyclic ammonia water;
Operation two, sedimentation oil removing
Stagnant ammonium remained ammonia continues to enter 2# adsorption and sedimentation oil eliminator 6, removes residu(al)tar further, sends in Stagnant ammonium remained ammonia groove 16 and collects;
Operation three, Stagnant ammonium decompose
Carry out heat exchange from the dense phenol water that the Stagnant ammonium remained ammonia of Stagnant ammonium remained ammonia groove 16 is first very high with the temperature of atmospheric distillation tower 13 extraction and then be admitted to the opening for feed on Stagnant ammonium decomposition tower 15 top; In Stagnant ammonium decomposition tower 15, the alkali lye generation neutralization reaction injected in the middle part of the Stagnant ammonium remained ammonia flowed into by tower top and tower, solid ammonium-salt decomposes, and is converted into ammonia steam, and the ammonium solution steam that ammonia steam and a small amount of sour gas are formed is discharged by Stagnant ammonium decomposition tower 15 tower top; Remaining ammonium solution waste water is discharged by tower reactor, the saltiness of ammonium solution waste water is higher, organic content is extremely low, directly deliver to other workshop sections by Stagnant ammonium decomposition tower waste water output channel 24, such as be directly used in continuous quenching, or for prepare tail gas desulfurization workshop section use lime milk solution or soda ash solution.
The tower reactor of Stagnant ammonium decomposition tower 15 provides heat by Stagnant ammonium decomposition tower well heater 11, and the origin of heat of Stagnant ammonium decomposition tower well heater 11 is the heat of ammonium solution waste water and the heat of stripped vapor.
(2) aftertreatment of free ammonia remained ammonia
Free ammonia phenol removal unit is made up of sedimentation oil removing, extraction oil removing, stripping dephenolize, distillation dephenolize, extracting and dephenolizing five operations, and main treatment facility comprises the 1# adsorption and sedimentation oil eliminator 5, extracting and dephenolizing tower 7, pressurization stripping tower 10 and the atmospheric distillation tower 13 that connect successively.
The detailed process of described free ammonia remained ammonia aftertreatment is:
Operation A, sedimentation oil removing
Free ammonia remained ammonia enters 1# adsorption and sedimentation oil eliminator 5, tentatively removes by absorption and settlement action the tar be mingled with in free ammonia remained ammonia;
Process B, extraction oil removing
Free ammonia remained ammonia from operation A is admitted to the opening for feed in the middle part of extraction oil removing dephenolize tower 7, and the extraction agent passed into bottom extracts, and described extraction agent is mixed by the crude benzol from crude benzol input channel 29 and the benzene light oil that contains from step D; By extraction, the residu(al)tar in free ammonia remained ammonia is removed further, removes a small amount of phenol simultaneously; Free ammonia remained ammonia through extraction oil removing is introduced into dephenolize remained ammonia groove 8, be then sent to free ammonia wastewater trough 9 keeps in, then enters operation C process;
Completing the overhead extraction of extraction agent by extracting and dephenolizing tower 7 of extraction, storing by entering oil product storage tank containing phenol crude benzol output channel 27;
Operation C, stripping dephenolize
Free ammonia remained ammonia from process B is divided into two parts by pipeline, and a part is directly admitted to the top of pressurization stripping tower 10, and another part first carries out heat exchange with treatment of wastewater from stripping, sends into the middle part of pressurization stripping tower 10 after intensification again.In pressurization stripping tower 10, free ammonia remained ammonia is to direction flowing at the bottom of tower, pressurized vapor is passed into by stripping tower 10 bottom of pressurizeing, is moved to tower top direction, contacted with the reverse of pressurized vapor by free ammonia remained ammonia, the organism such as ammonia and phenol is converted into mixing steam effusion, thus completes the deamination dephenolize to aqueous phase;
Mainly H is comprised by the stripping waste gas of the top extraction of pressurization stripping tower 10 2s, HCN, CO 2deng sour gas and a small amount of NH 3, go to yellow prussiate of potash production workshop section by pipeline and carry out deep processing.By the treatment of wastewater from stripping of extraction at the bottom of pressurization stripping tower 10 tower, first remove tar removing through 3# adsorption and sedimentation oil eliminator 17, then two portions are divided into use, part treatment of wastewater from stripping delivers to gas washing workshop section by 1# water stripping output channel 22, directly use as cyclic ammonia water, another part treatment of wastewater from stripping delivers to biochemical treatment workshop section by 2# water stripping output channel 23, carries out biochemical advanced treatment.Mainly comprise ammonia, phenol gas and tar gas by the stripped vapor of pressurization stripping tower 10 side take-off, enter step D process by pipeline;
Step D, distillation dephenolize
In order to make full use of the heat of high temperature of stripped vapor, two portions are divided into by stripped vapor to carry out heat exchange, self heat is transferred to Stagnant ammonium decomposition tower well heater 11 by heat exchange by a part, the distillation wastewater heat exchange of discharging at the bottom of another part and atmospheric distillation tower 13 tower, stripped vapor after heat exchange self is condensed into liquid, flows into stripping condensation liquid bath 12.
Stripping phlegma is admitted in the middle part of atmospheric distillation tower 13 by pipeline.In atmospheric distillation tower 13, stripping phlegma heat temperature raising, the most of free ammonia in stripping phlegma and part water are converted into distillation steam, and phenol is stayed in aqueous phase becomes dense phenol water.Dense phenol water is discharged by the outlet of atmospheric distillation tower 13 bottom, enter dense phenol tank 14 keeps in, and is then admitted to operation E process, is again sent into atmospheric distillation tower 13 carry out circulation and distill dephenolize by the distillation waste water of extraction at the bottom of tower and stripped vapor heat exchange after being heated up.
Distillation steam is discharged by atmospheric distillation tower 13 tower top, after deep cooling condensation, enter ammoniacal liquor light oil separator tank 30 carry out oily water separation, strong aqua concentration after separation, up to about 25%, is sent into anhydrous ammonia by strong aqua output channel 25 and is processed workshop section, as raw material production anhydrous ammonia; The isolated benzene light oil that contains delivers to crude benzol groove 28 by pipeline, mixes, use as extraction agent with the crude benzol from other unit;
Operation E, extracting and dephenolizing
The higher dense phenol water of temperature Stagnant ammonium remained ammonia that is first lower with temperature, that flowed out by Stagnant ammonium remained ammonia groove 16 carries out heat exchange, is then again returned in extracting and dephenolizing tower 7, and dense phenol water enters from the top of extracting and dephenolizing tower 7 and flows to direction at the bottom of tower; Meanwhile, by crude benzol and the extraction agent that form containing benzene light oil by entering bottom extracting and dephenolizing tower 7, moving to tower top direction, by the oily two alternate abundant contacts of water, complete and the phenol in dense phenol water and tar are extracted.
The extraction agent completing extraction, by the overhead extraction by extracting and dephenolizing tower 7, is introduced into and keeps in containing phenol crude benzol groove 26, then stores by entering oil product storage tank containing phenol crude benzol output channel 27, then carries out processing further reclaiming phenol; Gained dephenolize water mixes with the free ammonia remained ammonia completing extraction in process B, discharged by the outlet bottom extracting and dephenolizing tower 7 after enter dephenolize remained ammonia groove 8, and then enter pressurization stripping tower 10 carry out circulation phenol removal.
In the present invention, in 1# adsorption and sedimentation oil eliminator 5,2# adsorption and sedimentation oil eliminator 6, isolated tar is separated by reentering gas-liquid separator 1 after line-blending; The stripping waste gas of pressurization stripping tower 10 top effusion and the Stagnant ammonium decomposition tower 15 top ammonium solution steam of discharging by after line-blending, enter stripping retort gas output channel 21, drain into yellow prussiate of potash production workshop section, coproduction yellow prussiate of potash product.

Claims (6)

1. the dephenolization treating method of a residual coking ammonia water, raw gas sprays cooling through cyclic ammonia water, gas-liquid separator (1) is separated, be fixed ammonium remained ammonia and residual gas, residual gas continues to enter coal gas primary cooler (2) and cools, obtain free ammonia remained ammonia, it is characterized in that: described Stagnant ammonium remained ammonia enters Stagnant ammonium phenol removal unit and carries out aftertreatment, described free ammonia remained ammonia enters free ammonia phenol removal unit and carries out aftertreatment;
Described Stagnant ammonium phenol removal unit comprises oily water separation, sedimentation oil removing and Stagnant ammonium and decomposes three operations, and treatment facility comprises mechanical settling tank (3), 2# adsorption and sedimentation oil eliminator (6) and Stagnant ammonium decomposition tower (15);
Described free ammonia phenol removal unit comprises sedimentation oil removing, extraction oil removing, stripping dephenolize, distillation dephenolize, extracting and dephenolizing five operations, and treatment facility comprises 1# adsorption and sedimentation oil eliminator (5), extracting and dephenolizing tower (7), pressurization stripping tower (10) and atmospheric distillation tower (13).
2. the dephenolization treating method of a kind of residual coking ammonia water according to claim 1, is characterized in that the detailed process of described Stagnant ammonium remained ammonia aftertreatment is:
Operation one, oily water separation
First Stagnant ammonium remained ammonia enters mechanical settling tank (3) and carries out oily water separation, the tar be mingled with in removing Stagnant ammonium remained ammonia;
Operation two, sedimentation oil removing
The Stagnant ammonium remained ammonia obtained by operation one enters 2# adsorption and sedimentation oil eliminator (6), removes residu(al)tar further;
Operation three, Stagnant ammonium decompose
Stagnant ammonium remained ammonia after oil removing is admitted to Stagnant ammonium decomposition tower (15) top; In Stagnant ammonium decomposition tower (15), Stagnant ammonium remained ammonia and alkali lye react, Stagnant ammonium decomposes and is converted into ammonia steam, drains into other workshop sections by Stagnant ammonium decomposition tower (15) tower top, delivers to other workshop sections utilize by the ammonium solution waste water of discharging at the bottom of Stagnant ammonium decomposition tower (15) tower.
3. the dephenolization treating method of a kind of residual coking ammonia water according to claim 1, is characterized in that the detailed process of described free ammonia remained ammonia aftertreatment is:
Operation A, sedimentation oil removing
Free ammonia remained ammonia enters 1# adsorption and sedimentation oil eliminator (5), by the tar be mingled with in adsorption and sedimentation removing free ammonia remained ammonia;
Process B, extraction oil removing
Free ammonia remained ammonia from operation A is admitted to the middle part of extracting and dephenolizing tower (7), and the extraction agent passed into bottom extracts, further removing residu(al)tar and a small amount of phenol;
Operation C, stripping dephenolize
Free ammonia remained ammonia from process B is admitted to pressurization stripping tower (10) top, and the pressurized vapor passed into pressurization stripping tower (10) bottom interacts, and completes the deamination dephenolize of free ammonia remained ammonia; Stripped vapor is by the side take-off of the stripping tower that pressurizes (10);
Step D, distillation dephenolize
Stripped vapor through cooling be condensed into stripping phlegma, be admitted to atmospheric distillation tower (13) middle part; By heating, the free ammonia in stripping phlegma and part water are converted into gas, are discharged by atmospheric distillation tower (13) tower top, and phenol is stayed in aqueous phase becomes dense phenol water, discharged by the bottom of atmospheric distillation tower (13);
Operation E, extracting and dephenolizing
Dense phenol water from step D is again returned to extracting and dephenolizing tower (7), is entered by the opening for feed on extracting and dephenolizing tower (7) top, phenol in dense phenol water and tar extraction are in extraction agent, and dephenolize water enters pressurization stripping tower (10) by dephenolize remained ammonia groove (8) and carries out circulation phenol removal.
4. the dephenolization treating method of a kind of residual coking ammonia water according to claim 2, is characterized in that: the isolated tar of described operation one enters oil product storage tank by tar output channel (19) and stores; Be provided with the cyclic ammonia water output channel (20) be connected with coke oven collecting main in the middle and upper part of mechanical settling tank (3), the part in Stagnant ammonium remained ammonia directly cools to raw gas as cyclic ammonia water;
In described operation three, first Stagnant ammonium remained ammonia carries out heat exchange with the dense phenol water of atmospheric distillation tower (13) extraction, then is admitted to the top of Stagnant ammonium decomposition tower (15); Alkali lye is injected by the middle part of Stagnant ammonium decomposition tower (15); The heat of Stagnant ammonium decomposition tower (15) tower reactor is from ammonium solution waste water and stripped vapor.
5. the dephenolization treating method of a kind of residual coking ammonia water according to claim 3, is characterized in that:
In described operation C, free ammonia remained ammonia is divided into two portions by pipeline, and a part is directly admitted to the top of pressurization stripping tower (10), and another part first carries out heat exchange with treatment of wastewater from stripping and then is admitted to the middle part of stripping tower (10) of pressurizeing; The stripping waste gas of being overflowed by pressurization stripping tower (10) top goes to other workshop sections by pipeline and carries out deep processing; After 3# adsorption and sedimentation oil eliminator (17) oil removing, two portions are divided into by the treatment of wastewater from stripping of discharging at the bottom of pressurization stripping tower (10) tower, part treatment of wastewater from stripping is delivered to gas washing workshop section through 1# water stripping output channel (22), and another part treatment of wastewater from stripping is delivered to biochemical treatment workshop section through 2# water stripping output channel (23);
In described step D, the gas mixture of being discharged by atmospheric distillation tower (13) tower top enters ammoniacal liquor light oil separator tank (30) and carries out oily water separation after sub-zero treatment, obtains strong aqua and contains benzene light oil; Gained strong aqua sends into post-treatment workshop section by strong aqua output channel (25); Gained containing benzene light oil be transported to crude benzol groove (28), mix with crude benzol after use as extraction agent;
In described process B and operation E, the extraction agent from crude benzol groove (28) is entered by the bottom of extracting and dephenolizing tower (7), by the overhead extraction of extracting and dephenolizing tower (7), then store through entering oil product storage tank containing phenol crude benzol output channel (27).
6. the dephenolization treating method of a kind of residual coking ammonia water according to claim 1, is characterized in that: the tar obtained in described 1# adsorption and sedimentation oil eliminator (5), 2# adsorption and sedimentation oil eliminator (6) is separated by reentering gas-liquid separator (1) after line-blending; After the ammonium solution vapor mixing that the stripping waste gas of pressurization stripping tower (10) top effusion and Stagnant ammonium decomposition tower (15) top are discharged, carry out deep processing through row of conduits to yellow prussiate of potash production workshop section.
CN201410233912.3A 2014-05-30 2014-05-30 A kind of dephenolization treating method of residual coking ammonia water CN104030486B (en)

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