CN105797562A - Two-section type double-ammonia-process integrated desulfurization and denitration system for coking flue gas - Google Patents

Two-section type double-ammonia-process integrated desulfurization and denitration system for coking flue gas Download PDF

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Publication number
CN105797562A
CN105797562A CN201610293501.2A CN201610293501A CN105797562A CN 105797562 A CN105797562 A CN 105797562A CN 201610293501 A CN201610293501 A CN 201610293501A CN 105797562 A CN105797562 A CN 105797562A
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ammonia
section
flue gas
pipeline
desulphurization denitration
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CN201610293501.2A
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CN105797562B (en
Inventor
汤志刚
王登富
温燕明
康春清
王杰
陈善龙
李桂花
孙兆俊
段德强
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Jinan Metallurgical & Chemical Equipment Co Ltd
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Jinan Metallurgical & Chemical Equipment Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D47/00Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/06Spray cleaning
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/60Simultaneously removing sulfur oxides and nitrogen oxides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/02Dust removal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/08Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/121Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing NH3 only (possibly in combination with NH4 salts)
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/20Reductants
    • B01D2251/206Ammonium compounds
    • B01D2251/2062Ammonia
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • 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
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The invention discloses a two-section type double-ammonia-process integrated desulfurization and denitration system for coking flue gas. The two-section type double-ammonia-process integrated desulfurization and denitration system comprises an in-furnace denitration system and a chimney, wherein the in-furnace denitration system is connected with a coking furnace which is connected with the chimney; the chimney is connected with a waste-heat boiler which is connected with a flue-gas reheater; the flue-gas reheater is connected with a flue-gas fan which is connected with a washing dust remover by a pipeline; the washing dust remover is connected with a washing circulation pump which is connected with a washing dust-removing cooler; the washing dust-removing cooler is connected with an inlet pipeline at the upper part of the washing dust remover which is connected with a pipeline reactor; the pipeline reactor is connected with an ozone generator and a desulfurization and denitration integrated tower; the top part of the desulfurization and denitration integrated tower is connected with the flue-gas reheater which is connected with the chimney; purified flue gas exhausted from the desulfurization and denitration integrated tower enters the flue-gas reheater to be heated, and then returns to the chimney to be exhausted at high altitude. The two-section type double-ammonia-process integrated desulfurization and denitration system disclosed by the invention is low in cost and high in efficiency.

Description

The double; two ammonia process integration desulfurization denitration system of coking flue gas two-part
Technical field
The present invention relates to coking stack gases purification technology field, particularly relate to double; two ammonia (ammonium) the method integration desulfurization denitration system of a kind of coking flue gas two-part.
Background technology
The desulphurization denitration of coking flue gas of the prior art processes and the process of ammonia-containing water has various ways, to reach energy recycling, to reduce energy consumption, reduce the purpose of environmental pollution and destruction, but these method and apparatus of the prior art have the disadvantage that the flue gas desulfurization and denitration method cost having in prior art is high, and such as high temperature method of the prior art and catalysis method method of denitration cost are high;Some desulfurization off sulfide effect are poor, residual quantity big, and clean-up effect is bad, and vapour phase amount of ammonia slip is many simultaneously, and environment and air are polluted.
The present invention be applicant on the basis that original applying number is 201510690115.2 patents of invention, by continuous technological innovation, reduce technological equipment investment and the operating cost of desulphurization denitration further.
Summary of the invention
The purpose of the present invention is exactly for solving existing flue gases of cock oven desulphurization denitration high expensive, investing problem bigger than normal, it is provided that double; two ammonia (ammonium) the method integration desulfurization denitration system of a kind of coking flue gas two-part.The present invention utilizes the self-produced ammonia of coking as alkali source, and flue gas is carried out desulphurization denitration purification, forms callable ammonium sulfate and ammonium nitrate is incorporated to the ammonium sulfate workshop section of coking flow process, be can value-added side-product by the element sulphur in stack gases and nitrogen cycling of elements;The present invention fully in conjunction with the outer denitration technology of denitration in the stove and stove, significantly reduces denitration cost;The present invention adopts the ammonia desulphurization denitration of variable concentrations, and strong aqua ammonia can form resource product, and weak ammonia reduces the vapour phase dividing potential drop of ammonia, reduces the escaping of ammonia;The present invention adopts integration apparatus, simultaneous SO_2 and NO removal, significantly reduces desulphurization denitration investment;The present invention utilizes hydrogen peroxide denitration in ozone stove outer denitration, tower, realizes the elimination of NOx at a lower temperature, significantly reduces denitration cost;The present invention utilizes coking flow process internal resource ammonium sulfate liquor washing flue gas; further avoid ammonia process of desulfurization denitration and would generally produce the phenomenon that free ammonia vapour phase is escaped; not only do not increase cost, and improve the inside networking degree of coking flow process, efficiently solve the escaping of ammonia phenomenon of desulphurization denitration process.
This invention address that the technical scheme of technical problem is:
nullThe double; two ammonia process integration desulfurization denitration system of a kind of coking flue gas two-part,Including denitration in the stove system、Chimney、Waste heat boiler、Smoke re-heater、Coke oven,Also include flue gas blower fan、Scrubber、Cleaning dust circulating pump、Cleaning dust cooler、Ozonator、Pipeline reactor、Desulphurization denitration integrated tower、Circulation oxidator,Described denitration in the stove system is connected with coke oven by dilution air line or dilution nitrogen pipeline,Coke oven is connected with chimney by coke oven flue gas pipeline,Chimney is connected with waste heat boiler by coke oven flue gas pipeline,Waste heat boiler is connected with smoke re-heater by flue after recovered flue gas high-temperature residual heat,Smoke re-heater is connected with flue gas blower fan by flue after reclaiming low temperature exhaust heat,Flue gas blower and pipeline is connected with scrubber,Scrubber bottom is connected with cleaning circulation pump by liquid pipe,Cleaning circulation pump is connected with cleaning dust cooler by lower liquid phase outlet conduit,Cleaning dust cooler is connected with scrubber upper entrance pipeline,Scrubber is connected with pipeline reactor by pipeline after cleaning dust,Pipeline reactor is connected with ozonator by ozone pipeline,Pipeline reactor is connected with desulphurization denitration integrated tower by flue after reacting,Flue gas after washing cooling is sufficiently mixed reaction with the ozone from ozonator in pipeline reactor,After nitric oxide in flue gases of cock oven is partly or entirely aoxidized,Send into desulphurization denitration integrated tower and carry out desulphurization denitration process;Desulphurization denitration integrated tower top is connected with smoke re-heater by flue after purifying, smoke re-heater is connected with chimney by purifying smoke pipeline, the purifying smoke discharging desulphurization denitration integrated tower enters smoke re-heater, before utilizing desulphurization denitration, the low temperature exhaust heat heating of flue gas is increased to 100-150 DEG C of return chimney, high altitude discharge.
Described desulphurization denitration integrated tower includes the two-stage nitration desulphurization denitration section at one section of desulphurization denitration section of bottom, middle part, and the top of two-stage nitration desulphurization denitration section is provided with catches ammonia section, catches ammonia section top and is provided with physical property demister.Described one section of desulphurization denitration section is connected with the scrubbing ammonia waterpipe of strong aqua ammonia pipeline or raw coke oven gas desulfurization regeneration tail gas, described strong aqua ammonia pipeline is connected with the strong aqua ammonia pipeline of coking ammonia still process workshop section, described scrubbing ammonia waterpipe is connected with the scrubbing ammonia waterpipe of raw coke oven gas desulfurization regeneration tail gas, and the washing ammonia from the strong aqua ammonia of coking ammonia still process workshop section or raw coke oven gas desulfurization regeneration tail gas adds one section of desulphurization denitration section as the alkali source of desulphurization denitration.One section of circulating pump is connected with desulphurization denitration integrated tower by one section of circulation ammonium liquid pipeline, one-step cooling device is connected by one section of circulation ammonium liquid pipeline and one section of circulating pump, one-step cooling device is connected with desulphurization denitration integrated tower by one section of circulation ammonium liquid pipeline, one section of desulphurization denitration section of desulphurization denitration integrated tower is connected with circulation oxidator by ammonium liquid side line pipeline, circulation cycle delivery side of pump is connected with circulation oxidator top by circulation cycle conduit upper, described circulation cycle conduit upper is provided with ejector near the position on circulation oxidator top, the import of circulation cycle pump is connected with bottom circulation oxidator by circulation cycle pipeline bottom, the ammonium sulfate after oxidation and ammonium nitrate mixed-ammonium salt solution being sent to the ammonium sulfate workshop section Resource recovery product of coking or are used for complex acid by spur outlet and pipeline of circulation cycle pump;
Described two-stage nitration desulphurization denitration section is connected by pipeline with the remained ammonia from coking ammonia still process workshop section, remained ammonia from coking ammonia still process workshop section adds two-stage nitration desulphurization denitration section by pipeline as the diluent of ammonia concentration, the bottom of described two-stage nitration desulphurization denitration section is connected with two-stage nitration pump inlet by two-stage nitration circulation fluid pipeline, two-stage nitration circulating-pump outlet is connected with two-step cooling device by two-stage nitration circulation fluid pipeline, and two-step cooling device is connected with the top of two-stage nitration desulphurization denitration section by two-stage nitration circulation fluid pipeline.Remained ammonia is sent to the ammonia still of the ammonia still process workshop section of coking by the spur outlet of two-stage nitration circulating pump by pipeline.
Described ammonia section of catching is connected with ammonium sulfate liquor pipeline, flue gas after two-stage nitration desulphurization denitration, what enter desulphurization denitration integrated tower top catches ammonia section, utilize the acid mother liquid washing flue gas of sulphuric acid workshop section, sulfur ammonium acid mother liquid washing flue gas returns ammonium sulfate workshop section after catching residue ammonia, and the control temperature catching ammonia section is 50-70 DEG C.
After described physical property demister intercepts power elimination flue gas acid mist by centrifugal force and inertia, flue gas is discharged from desulphurization denitration integrated tower top;Flue gas after catching ammonia section enters the physical property demister at desulphurization denitration integrated tower top, and after intercepting power elimination flue gas acid mist by centrifugal force and inertia, flue gas is discharged from desulphurization denitration integrated tower top;The temperature of described mist catching section controls as 50-60 DEG C.
Described ejector adopts venturi tube structure, ejector is connected with external air duct, the ejector circulation injection suction utilizing venturi tube structure is incorporated herein the air oxidant as circulation oxidator, sprayed the suction produced by the circulation of circulation cycle pump and introduce air, oxygen in air fully and ammonium liquid be sufficiently mixed reaction, ammonium sulfite therein is generated ammonium sulfate, then the mixed salt solution containing ammonium sulfate and ammonium nitrate is sent to the ammonium sulfate workshop section of coking, Resource recovery product, control temperature in described circulation oxidator and be 50-80 DEG C, pH controls as 6.0-6.8.
Flue gas after described dilution air line waste heat recovery or the flue gas after purification are dilution air, or are mixed into the 0-50% that mixed volume is air capacity of noble gas, flue gas or noble gas in atmosphere;Being mixed into low-heat value gas in heating gas, low-heat value gas mixed volume is the 0-70% of heating gas amount, reduces coke oven and discharges the amount of nitrogen oxides in flue gas, and making the amount of nitrogen oxides that coke oven is discharged in flue gas is 250-550mg/m3
Coke oven flue temperature after denitration in the stove system denitration processes is 220-350 DEG C, flue gases of cock oven is sent into waste heat boiler and is reclaimed flue gas high-temperature residual heat, the waste heat that waste heat boiler reclaims is used as to produce steam, or it is directly used in ammonia still process heating distilled ammonia wastewater, or heating conduction oil, after reclaiming high-temperature residual heat, effluent gas temperature is down to 150-200 DEG C;Reclaiming the flue gas after high-temperature residual heat through waste heat boiler and send into smoke re-heater recovery flue gases at low waste heat, the purification flue gas discharged by desulphurization denitration integrated tower is from 50-80 DEG C of heating to 100-150 DEG C, and own temperature is down to 90-130 DEG C;Flue gas after reclaiming low temperature exhaust heat sends into scrubber by flue gas blower fan, scrubber utilize cleaning circulation pump sprayed into from scrubber top by cycles of washing liquid, with fed from below into flue gas counter current contacting, dust impurity in washing elimination flue gas, flue gas is cooled to 60-80 DEG C further.
Flue gas after washing cooling is sufficiently mixed reaction with the ozone from ozonator in pipeline reactor, after partly or entirely being aoxidized by the nitric oxide in flue gases of cock oven, sends into desulphurization denitration integrated tower and carries out desulphurization denitration process.
Add hydrogen peroxide carry out oxidation in one section of described desulphurization denitration section, two-stage nitration desulphurization denitration section.Strengthening denitration efficiency, reduces ozone-depleting, reduces operating cost.
Beneficial effects of the present invention:
1. the present invention utilizes the self-produced ammonia of coking as alkali source, and flue gas is carried out desulphurization denitration purification, forms callable ammonium sulfate and ammonium nitrate is incorporated to the ammonium sulfate workshop section of coking flow process, be can value-added side-product by the element sulphur in stack gases and nitrogen cycling of elements;Do not produce solid waste and pollution transportation.
2. the present invention is fully in conjunction with the outer denitration technology of denitration in the stove and stove, and denitration in the stove adopts dilution air to combine with the measure of dilution coal gas, significantly reduces denitration cost.
3. the present invention adopts the ammonia desulphurization denitration of variable concentrations, strong aqua ammonia can form resource product, weak ammonia reduces the vapour phase dividing potential drop of ammonia, reduce the escaping of ammonia, close with the close Rhizoma Nelumbinis of the existing ammonium sulfate workshop section of coking and ammonia still process workshop section simultaneously and be connected, make full use of and excavated automatically cleaning and the self-purification function of coking flow process;Construction investment and operating cost are greatly reduced.
4. the present invention adopts integration apparatus, simultaneous SO_2 and NO removal, generate resource product, two-stage nitration desulphurization denitration and ammonium sulfate liquor by one section of desulphurization denitration and catch ammonia section elimination the escaping of ammonia, mist catching section elimination acid mist, not only complete the integrated of several functions, enhance desulphurization and denitration, catch ammonia, except fog effect, also significantly reduce desulphurization denitration investment;Improve flue gases of cock oven degree of purification and environmental quality.
5. patent of the present invention adopts oxidizing process to utilize the outer denitration of ozone stove, it is possible to fully recycling flue gases of cock oven waste heat, and realizes the elimination of nitrogen oxides at a lower temperature, can effectively reduce denitration cost;Add hydrogen peroxide by one section of desulphurization denitration section, two-stage nitration desulphurization denitration section and carry out oxidation, strengthen denitration efficiency, reduce ozone-depleting, reduce operating cost.
6. the present invention has fully reclaimed the UTILIZATION OF VESIDUAL HEAT IN of flue gas.Utilize waste heat boiler to reclaim high-temperature residual heat, byproduct steam, or directly heat distilled ammonia wastewater, or heating conduction oil;Flue gas after utilizing low temperature exhaust heat heating desulphurization denitration to purify, effectively eliminates the dew point corrosion of flue gas, takes full advantage of the high altitude discharge advantage of original chimney.Coking flow process internal resource ammonium sulfate liquor washing flue gas is utilized by profit; further avoid ammonia process of desulfurization denitration and would generally produce the phenomenon that free ammonia vapour phase is escaped; not only do not increase cost, and improve the inside networking degree of coking flow process, efficiently solve the escaping of ammonia phenomenon of desulphurization denitration process.
7. the present invention develops circulation oxidator, effectively improves sulfite oxidation effect.
Accompanying drawing explanation
Fig. 1 is the structural representation of invention.
Detailed description of the invention
In order to be more fully understood that the present invention, explain in detail embodiments of the present invention below in conjunction with accompanying drawing.
As shown in Figure 1, the double; two ammonia process integration desulfurization denitration system of a kind of coking flue gas two-part, including denitration in the stove system 1, chimney 2, waste heat boiler 3, smoke re-heater 4, flue gas blower fan 5, scrubber 6, cleaning dust circulating pump 7, cleaning dust cooler 8, ozonator 9, pipeline reactor 10,11, one section of circulating pump 12 of desulphurization denitration integrated tower, one-step cooling device 13, two-stage nitration circulating pump 14, two-step cooling device 15, circulation oxidator 16, circulation cycle pump 17, penetrates haustorium 18, coke oven 19.nullDescribed denitration in the stove system 1 is connected with coke oven 19 by dilution air line 29 and dilution gas piping 28,Coke oven 19 is connected with chimney 2 by coke oven flue gas pipeline,Chimney 2 is connected with waste heat boiler 3 by coke oven flue gas pipeline,Waste heat boiler 3 is connected with smoke re-heater 4 by flue after recovered flue gas high-temperature residual heat,Smoke re-heater 4 is connected with flue gas blower fan 5 by flue after reclaiming low temperature exhaust heat,Flue gas blower fan 5 is connected with scrubber 6 by pipeline,Scrubber 6 bottom is connected with cleaning circulation pump 7 by liquid pipe,Cleaning circulation pump 7 is connected with cleaning dust cooler 8 by lower liquid phase outlet conduit,Cleaning dust cooler 8 is connected with scrubber 6 upper entrance pipeline,Scrubber 6 is connected with pipeline reactor 10 by pipeline after cleaning dust,Pipeline reactor 10 is connected with ozonator 9 by ozone pipeline,Pipeline reactor 10 is connected with desulphurization denitration integrated tower 11 by flue after reacting.Desulphurization denitration integrated tower 11 top is connected with smoke re-heater 4 by flue after purifying, and smoke re-heater 4 is connected with chimney 2 by purifying smoke pipeline.The purifying smoke discharging desulphurization denitration integrated tower enters smoke re-heater, and before utilizing desulphurization denitration, the low temperature exhaust heat heating of flue gas is increased to 100-150 DEG C, returns chimney, high altitude discharge.
Described desulphurization denitration integrated tower includes the two-stage nitration desulphurization denitration section at one section of desulphurization denitration section of bottom, middle part, and the top of two-stage nitration desulphurization denitration section is provided with catches ammonia section, catches ammonia section top and is provided with physical property demister.Described one section of desulphurization denitration section is connected with the scrubbing ammonia waterpipe 20 of strong aqua ammonia pipeline 21 or raw coke oven gas desulfurization regeneration tail gas, described strong aqua ammonia pipeline is connected with the strong aqua ammonia pipeline of coking ammonia still process workshop section, described scrubbing ammonia waterpipe is connected with the scrubbing ammonia waterpipe of raw coke oven gas desulfurization regeneration tail gas, and the washing ammonia from the strong aqua ammonia of coking ammonia still process workshop section or coal oven dithio-gas desulfurization regeneration tail gas adds one section of desulphurization denitration section as the alkali source of desulphurization denitration.nullOne section of circulating pump 12 is connected with desulphurization denitration integrated tower 11 by one section of circulation ammonium liquid pipeline,One-step cooling device 13 is connected by one section of circulation ammonium liquid pipeline and one section of circulating pump 12,One-step cooling device 13 is connected with desulphurization denitration integrated tower 11 by one section of circulation ammonium liquid pipeline,One section of desulphurization denitration section of desulphurization denitration integrated tower 11 is connected with circulation oxidator 16 by ammonium liquid side line pipeline,The outlet of circulation cycle pump 17 is connected with circulation oxidator 16 top by circulation cycle pipeline 30 top,Described circulation cycle pipeline 30 top is provided with ejector 18 near the position on circulation oxidator 16 top,The import of circulation cycle pump 17 is connected with bottom circulation oxidator 16 by circulation cycle pipeline bottom,Ammonium sulfate after oxidation and ammonium nitrate mixed-ammonium salt solution are sent to the ammonium sulfate workshop section 27 Resource recovery product of coking or are used for complex acid by spur outlet and pipeline by circulation cycle pump 17.
Described two-stage nitration desulphurization denitration section is connected by pipeline 22 with the remained ammonia from coking ammonia still process workshop section, remained ammonia from coking ammonia still process workshop section adds two-stage nitration desulphurization denitration section by pipeline 22 as the diluent of ammonia concentration, the bottom of described two-stage nitration desulphurization denitration section is connected with two-stage nitration circulating pump 14 import by two-stage nitration circulation fluid pipeline, two-stage nitration circulating pump 14 is exported and is connected with two-step cooling device 15 by two-stage nitration circulation fluid pipeline, and two-step cooling device 15 is connected with the top of two-stage nitration desulphurization denitration section by two-stage nitration circulation fluid pipeline.Remained ammonia is sent to the ammonia still 25 of the ammonia still process workshop section of coking by the spur outlet of two-stage nitration circulating pump 14 by pipeline.
In two-stage nitration desulphurization denitration section, add two-stage nitration desulphurization denitration section from the remained ammonia before coking ammonia still process workshop section ammonia still, dilute from ammonia vapour phase concentration in the flue gas after one section of desulphurization denitration section.Most of surplus ammonia sends into two-stage nitration recirculation cooler by two-stage nitration circulating pump, control after temperature through one section of recirculation cooler, two-stage nitration desulphurization denitration section is added from the top of one section of desulphurization denitration tower, with enter from two-stage nitration desulphurization denitration pars infrasegmentalis, from the flue gases of cock oven counter current contacting of one section of desulphurization denitration section, complete the elimination of remaining sulfur dioxide and nitrogen oxides on the one hand, reduce the ammonia dividing potential drop in gas phase on the other hand, control the escaping of ammonia.According to the principle of material balance, small part circulation fluid returns the ammonia still of coking ammonia still process workshop section.The control temperature of one section of desulphurization denitration section is 50-80 DEG C, and pH controls as 5.5-6.2.
Add hydrogen peroxide carry out oxidation in one section of described desulphurization denitration section, two-stage nitration desulphurization denitration section.In tower, add hydrogen peroxide oxidation effect, improve denitration efficiency, it is possible to reduce ozone usage, reduce operating cost.
Described ammonia section of catching is connected with ammonium sulfate liquor pipeline 23, and the flue gas after utilizing the ammonium sulfate liquor washing two-stage desulfurization of sulphuric acid workshop section to purify, ammonium sulfate liquor washing flue gas returns ammonium sulfate workshop section 24 by pipeline after catching residue ammonia.Flue gas after two-stage nitration desulphurization denitration, what enter desulphurization denitration integrated tower top catches ammonia section, utilizes the acid mother liquid washing flue gas of ammonium sulfate workshop section, and acid mother liquid washing flue gas returns ammonium sulfate workshop section after catching residue ammonia.The control temperature catching ammonia section is 50-70 DEG C.If by after two-stage nitration desulphurization denitration, the ammonia content in flue gas is up to standard, and this catches ammonia section and as standby measure, can not put into operation.
After described physical property demister intercepts power elimination flue gas acid mist by centrifugal force and inertia, flue gas is discharged from desulphurization denitration integrated tower 11 top.Flue gas after catching ammonia section enters the demister at desulphurization denitration integrated tower top, after intercepting power elimination flue gas acid mist by centrifugal force and inertia, flue gas is discharged from desulphurization denitration integrated tower top, enter smoke re-heater, after before utilizing desulphurization denitration, the low temperature exhaust heat of flue gas heats, return chimney, high altitude discharge.The temperature of mist catching section controls as 50-60 DEG C.
Described ejector 18 adopts venturi tube structure, and ejector 18 is connected with external air duct 26, utilizes the ejector 18 circulation injection suction of venturi tube structure to be incorporated herein the air oxidant as circulation oxidator.In circulation oxidator, being sprayed the suction produced by the circulation of circulation cycle pump and introduce air, abundant and ammonium liquid is sufficiently mixed reaction, and ammonium sulfite therein is generated ammonium sulfate, the mixed salt solution containing ammonium sulfate and ammonium nitrate the most at last is sent to the ammonium sulfate workshop section of coking, Resource recovery product.Controlling temperature in circulation oxidator and be 50-100 DEG C, pH controls as 6.0-6.8.
Described dilution air line 29 is dilution air by the flue gas after the flue gas after waste heat recovery or purification, or is mixed into noble gas in atmosphere, and the mixed volume of described flue gas or noble gas is the 0-50% of air capacity;Heating gas is mixed into low-heat value gas, such as dilution coal gas measures such as blast furnace gas, vaporization coal gas and water coal gas, mixed volume is the 0-70% of heating gas amount, reduces coke oven and discharges the amount of nitrogen oxides in flue gas, and making the amount of nitrogen oxides that coke oven is discharged in flue gas is 250-550mg/M3.
Coke oven flue temperature after denitration in the stove system 1 denitration processes is 220-350 DEG C, flue gases of cock oven is sent into waste heat boiler and is reclaimed flue gas high-temperature residual heat, the waste heat that waste heat boiler reclaims is used as to produce steam, or it is directly used in ammonia still process heating distilled ammonia wastewater, or heating conduction oil, after reclaiming high-temperature residual heat, effluent gas temperature is down to 150-200 DEG C;Reclaiming the flue gas after high-temperature residual heat through waste heat boiler and send into smoke re-heater recovery flue gases at low waste heat, the purification flue gas discharged by desulphurization denitration integrated tower is from 50-80 DEG C of heating to 100-150 DEG C, and own temperature is down to 90-130 DEG C;Flue gas after reclaiming low temperature exhaust heat sends into scrubber by flue gas blower fan, scrubber utilize cleaning circulation pump sprayed into from scrubber top by cycles of washing liquid, with fed from below into flue gas counter current contacting, dust impurity in washing elimination flue gas, flue gas is cooled to 60-80 DEG C further.The dust obtained after spray is enriched with at scrubber bottom precipitation, regularly discharges it, as fixed-end forces.Cycles of washing liquid can use clear water, the outer draining of available cycles, it is also possible to waste water after waste water or biochemical treatment after ammonia still process.
Flue gas after washing cooling is sufficiently mixed reaction with the ozone from ozonator in pipeline reactor, after partly or entirely being aoxidized by the nitric oxide in flue gases of cock oven, sends into desulphurization denitration integrated tower and carries out desulphurization denitration process.According to technique needs, this oxidation reactor may also placed in and realizes oxidation reaction function in desulphurization denitration integrated tower.
One section of desulphurization denitration section, strong aqua ammonia or coke oven gas desulfurization regenerator top cleaning mixture from coking ammonia still process workshop section add one section of desulphurization denitration section, sulfur dioxide and reaction of nitrogen oxides in flue gases of cock oven is sent into from one section of desulphurization denitration section, generate the solution of ammonium sulfite and ammonium nitrate, major part ammonium salt solution sends into one section of recirculation cooler by one section of circulating pump, control after temperature through one section of recirculation cooler, one section of desulphurization denitration section is added from the top of one section of desulphurization denitration tower, with the flue gases of cock oven counter current contacting from one section of desulphurization denitration pars infrasegmentalis, complete desulphurization denitration process.According to the principle of material balance, small part ammonium liquid is sent into circulation oxidator and is aoxidized further.The control temperature of one section of desulphurization denitration section is 50-80 DEG C, and pH controls as 5.8-6.5.
In circulation oxidator, sprayed the suction produced by the circulation of circulation cycle pump, introduce air, abundant and ammonium liquid is sufficiently mixed reaction, ammonium sulfite therein is generated ammonium sulfate, and the mixed salt solution containing ammonium sulfate and ammonium nitrate the most at last is sent to the ammonium sulfate workshop section of coking, Resource recovery product.Controlling temperature in circulation oxidator and be 50-80 DEG C, pH controls as 6.0-6.8.
Technical specification after present invention process is as follows:
Index after gas cleaning
SO2:≤50mg/Nm3
NOX:≤100mg/Nm3
NH3:≤1mg/Nm3
Dust content :≤5mg/Nm3
Sulphuric acid mist content :≤5mg/Nm3
The detailed description of the invention of invention is described in conjunction with accompanying drawing although above-mentioned; but not limiting the scope of the invention; on the basis of technical scheme, those skilled in the art need not pay various amendments or deformation that creative work can make still within protection scope of the present invention.

Claims (6)

  1. null1. the double; two ammonia process integration desulfurization denitration system of coking flue gas two-part,Including denitration in the stove system、Chimney、Waste heat boiler、Smoke re-heater、Coke oven,It is characterized in that,Also include flue gas blower fan、Scrubber、Cleaning dust circulating pump、Cleaning dust cooler、Ozonator、Pipeline reactor、Desulphurization denitration integrated tower、Circulation oxidator,Described denitration in the stove system is connected with coke oven by dilution air line and dilution gas piping,Coke oven is connected with chimney by coke oven flue gas pipeline,Chimney is connected with waste heat boiler by coke oven flue gas pipeline,Waste heat boiler is connected with smoke re-heater by flue after recovered flue gas high-temperature residual heat,Smoke re-heater is connected with flue gas blower fan by flue after reclaiming low temperature exhaust heat,Flue gas blower and pipeline is connected with scrubber,Scrubber bottom is connected with cleaning circulation pump by liquid pipe,Cleaning circulation pump is connected with cleaning dust cooler by lower liquid phase outlet conduit,Cleaning dust cooler is connected with scrubber upper entrance pipeline,Scrubber is connected with pipeline reactor by pipeline after cleaning dust,Pipeline reactor is connected with ozonator by ozone pipeline,Pipeline reactor is connected with desulphurization denitration integrated tower by flue after reacting,Flue gas after washing cooling is sufficiently mixed reaction with the ozone from ozonator in pipeline reactor,After nitric oxide in flue gases of cock oven is partly or entirely aoxidized,Send into desulphurization denitration integrated tower and carry out desulphurization denitration process;Desulphurization denitration integrated tower top is connected with smoke re-heater by flue after purifying, smoke re-heater is connected with chimney by purifying smoke pipeline, the purifying smoke discharging desulphurization denitration integrated tower enters smoke re-heater, before utilizing desulphurization denitration, the low temperature exhaust heat heating of flue gas is increased to 100-150 DEG C of return chimney, high altitude discharge.
  2. null2. the double; two ammonia process integration desulfurization denitration system of coking flue gas two-part as claimed in claim 1,It is characterized in that,Described desulphurization denitration integrated tower includes one section of desulphurization denitration section of bottom、The two-stage nitration desulphurization denitration section at middle part,The top of two-stage nitration desulphurization denitration section is provided with catches ammonia section,Catch ammonia section top and be provided with physical property demister,Described one section of desulphurization denitration section is connected with the scrubbing ammonia waterpipe of strong aqua ammonia pipeline or raw coke oven gas desulfurization regeneration tail gas,Described strong aqua ammonia pipeline is connected with the strong aqua ammonia pipeline of coking ammonia still process workshop section,Described scrubbing ammonia waterpipe is connected with the scrubbing ammonia waterpipe of raw coke oven gas desulfurization regeneration tail gas,Washing ammonia from the strong aqua ammonia of coking ammonia still process workshop section or raw coke oven gas desulfurization regeneration tail gas adds one section of desulphurization denitration section as the alkali source of desulphurization denitration,One section of circulating pump is connected with desulphurization denitration integrated tower by one section of circulation ammonium liquid pipeline,One-step cooling device is connected by one section of circulation ammonium liquid pipeline and one section of circulating pump,One-step cooling device is connected with desulphurization denitration integrated tower by one section of circulation ammonium liquid pipeline,One section of desulphurization denitration section of desulphurization denitration integrated tower is connected with circulation oxidator by ammonium liquid side line pipeline,Circulation cycle delivery side of pump is connected with circulation oxidator top by circulation cycle conduit upper,Described circulation cycle conduit upper is provided with ejector near the position on circulation oxidator top,The import of circulation cycle pump is connected with bottom circulation oxidator by circulation cycle pipeline bottom,Ammonium sulfate after oxidation and ammonium nitrate mixed-ammonium salt solution are sent to the ammonium sulfate workshop section Resource recovery product of coking or are used for complex acid by spur outlet and pipeline by circulation cycle pump;
    Described two-stage nitration desulphurization denitration section is connected by pipeline with the remained ammonia from coking ammonia still process workshop section, remained ammonia from coking ammonia still process workshop section adds two-stage nitration desulphurization denitration section by pipeline as the diluent of ammonia concentration, the bottom of described two-stage nitration desulphurization denitration section is connected with two-stage nitration pump inlet by two-stage nitration circulation fluid pipeline, two-stage nitration circulating-pump outlet is connected with two-step cooling device by two-stage nitration circulation fluid pipeline, two-step cooling device is connected with the top of two-stage nitration desulphurization denitration section by two-stage nitration circulation fluid pipeline, remained ammonia is sent to the ammonia still of the ammonia still process workshop section of coking by the spur outlet of two-stage nitration circulating pump by pipeline;
    Described ammonia section of catching is connected with ammonium sulfate liquor pipeline, flue gas after two-stage nitration desulphurization denitration, what enter desulphurization denitration integrated tower top catches ammonia section, utilize the acid mother liquid washing flue gas of sulphuric acid workshop section, sulfur ammonium acid mother liquid washing flue gas returns ammonium sulfate workshop section after catching residue ammonia, and the control temperature catching ammonia section is 50-70 DEG C;
    After described physical property demister intercepts power elimination flue gas acid mist by centrifugal force and inertia, flue gas is discharged from desulphurization denitration integrated tower top;Flue gas after catching ammonia section enters the physical property demister at desulphurization denitration integrated tower top, after intercepting power elimination flue gas acid mist by centrifugal force and inertia, flue gas is discharged from desulphurization denitration integrated tower top, enter smoke re-heater, after before utilizing desulphurization denitration, the low temperature exhaust heat of flue gas heats, return chimney, high altitude discharge;The temperature of described mist catching section controls as 50-60 DEG C.
  3. 3. the double, two ammonia process integration desulfurization denitration system of coking flue gas two-part as claimed in claim 1, it is characterized in that, described ejector adopts venturi tube structure, ejector is connected with external air duct, the ejector circulation injection suction utilizing venturi tube structure is incorporated herein the air oxidant as circulation oxidator, sprayed the suction produced by the circulation of circulation cycle pump and introduce air, oxygen in air fully and ammonium liquid be sufficiently mixed reaction, ammonium sulfite therein is generated ammonium sulfate, then the mixed salt solution containing ammonium sulfate and ammonium nitrate is sent to the ammonium sulfate workshop section of coking, Resource recovery product, control temperature in described circulation oxidator and be 50-80 DEG C, pH controls as 6.0-6.8.
  4. 4. the double; two ammonia process integration desulfurization denitration system of coking flue gas two-part as claimed in claim 1, it is characterized in that, flue gas after described dilution air line waste heat recovery or the flue gas after purification are dilution air, or it is mixed into the 0-50% that mixed volume is air capacity of noble gas, flue gas or noble gas in atmosphere;Being mixed into low-heat value gas in heating gas, low-heat value gas mixed volume is the 0-70% of heating gas amount, reduces coke oven and discharges the amount of nitrogen oxides in flue gas, and making the amount of nitrogen oxides that coke oven is discharged in flue gas is 250-550mg/m3
  5. 5. the double; two ammonia process integration desulfurization denitration system of coking flue gas two-part as described in claim 1 or 2, it is characterized in that, coke oven flue temperature after denitration in the stove system denitration processes is 220-350 DEG C, flue gases of cock oven is sent into waste heat boiler and is reclaimed flue gas high-temperature residual heat, the waste heat that waste heat boiler reclaims is used as to produce steam, or it is directly used in ammonia still process heating distilled ammonia wastewater or heating conduction oil, reclaim high-temperature residual heat rear pass temperature and be down to 150-200 DEG C;Reclaiming the flue gas after high-temperature residual heat through waste heat boiler and send into smoke re-heater recovery flue gases at low waste heat, the purification flue gas discharged by desulphurization denitration integrated tower is from 50-80 DEG C of heating to 100-150 DEG C, and own temperature is down to 90-130 DEG C;Flue gas after reclaiming low temperature exhaust heat sends into scrubber by flue gas blower fan, scrubber utilize cleaning circulation pump sprayed into from scrubber top by cycles of washing liquid, with fed from below into flue gas counter current contacting, dust impurity in washing elimination flue gas, flue gas is cooled to 60-80 DEG C further.
  6. 6. the double; two ammonia process integration desulfurization denitration system of coking flue gas two-part as claimed in claim 2, is characterized in that, adds hydrogen peroxide carry out oxidation in one section of described desulphurization denitration section, two-stage nitration desulphurization denitration section.
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CN106621768A (en) * 2016-12-20 2017-05-10 亚太环保股份有限公司 Ammonia process of desulfurization integral purification device and method for acid gas sulfur recovery tail gas
CN108970352A (en) * 2018-06-19 2018-12-11 山东师范大学 A kind of flue gas low-temperature denitration method
CN110505909A (en) * 2017-02-15 2019-11-26 通用电气技术有限公司 For improving the oxidation control of flue gas desulfurization performance
CN111068492A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Coking tail gas treatment process and device

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CN108970352A (en) * 2018-06-19 2018-12-11 山东师范大学 A kind of flue gas low-temperature denitration method
CN111068492A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Coking tail gas treatment process and device
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Denomination of invention: Integrated desulfurization and denitrification system for coking flue gas using two-stage double ammonia process

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