CN108786441A - Coke oven flue gas electromigration desulfurization sulphur technique - Google Patents
Coke oven flue gas electromigration desulfurization sulphur technique Download PDFInfo
- Publication number
- CN108786441A CN108786441A CN201810556138.8A CN201810556138A CN108786441A CN 108786441 A CN108786441 A CN 108786441A CN 201810556138 A CN201810556138 A CN 201810556138A CN 108786441 A CN108786441 A CN 108786441A
- Authority
- CN
- China
- Prior art keywords
- gas
- flue gas
- coke oven
- electromigration
- claus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/22—Separation 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 by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Treating Waste Gases (AREA)
- Industrial Gases (AREA)
Abstract
The invention discloses a kind of coke oven flue gas electromigration desulfurization sulphur techniques, belong to the energy conservation and environmental protection field of coking industry.Include the coke oven flue gas from coke oven horizontal flue enter sulfur dioxide electromigration membrane separator it is isolated be rich in SO2Gas and de- SO2Flue gas afterwards takes off SO2Flue gas, which enters to be sent into SCR denitration reactor after heater heat temperature raising, afterwards completes denitration, and flue gas is sent into row outside chimney after waste heat recovery after denitration；Rich in SO2Gas is rich in H with from hydrogen sulfide Analytic Tower2S gases are sent into the Claus tail gases that claus oven reaction generates sulfur-bearing steam together, the Claus tail gases of sulfur-bearing steam enter sulfur condenser lowered temperature reclamation sulphur, Claus tail gases are divided into 3 parts after cooling, enter hydrogen sulfide Analytic Tower as H after a part of tail gas cooling section heat exchange heating for entering claus oven2S desorber air lift air sources and heat source, another part enter sulfur dioxide electromigration membrane separator as coke oven flue gas electromigration desulfurization carrier gas after dedusting, and remainder is incorporated to coal oven dithio-gas pipe network.The technique that the present invention designs can be in effective recycling coke oven flue gas amounts of sulphur contaminants.
Description
Technical field
The present invention relates to coke oven flue gas desulfurization and the recyclings of Sulphur ressource, belong to the energy conservation and environmental protection field of coking industry,
More particularly to a kind of coke oven flue gas electromigration desulfurization sulphur technique.
Background technology
Currently, the coke oven flue gas desulfurizing and denitrifying process run at home：Semi-dry desulphurization+low-temperature SCR selective catalysis is also
Former denitration dust-removing integrated technique, desulfurization and denitrification integral technology (activated coke method), moving bed dry desulfurization+low temperature SCR denitration
Technology, new catalytic method flue gas desulfurization and denitrification technology, the ammonia process of desulfurization+Ozonation denitration technology, what is selected is first desulfurization
The technology of denitration again, although in operation also this or that the problem of, overall operation is steady.
The arrangement of the first desulfurization of selection denitration again, dry method, semi-dry desulfurizing process are configurable to select SCR denitration technique,
If enterprise has selected wet desulfurizing process, there are two schemes for current technology：One is the cigarette after desulfurizer is handled
Temperature degree first passes through heat-exchanger rig flue-gas temperature is increased to 180 DEG C or more and enter back into flue gas SCR denitration device at 60~80 DEG C
Processing, this scheme is worthless from the aspect of energy consumption, is also worthless in economy.Second scheme is that wet method is de-
Sulphur technique+Ozonation denitrating technique, the program can meet the order of placement of first desulfurization denitration again, and can be effectively by cigarette
SO in gas pollutant2, NOx controls in acceptability limit, but up to the present yet there are no successful operation Case Report.
The selection of coke oven flue gas desulphurization denitration configuration sequence must be prudent for enterprise, because it is related to desulphurization denitration dress
Set whether can continuous and steady operation, flue gas pollutant concentration of emission whether can stably reaching standard, and be to determine the characteristics of coke oven flue gas
One of qualitative factor.
One coke-oven plant of Shaanxi selects SCR denitration+ammonia desulfurizing process, denitrification apparatus to be unable to continuous and steady operation always, takes off
Nitre device be arranged in caused by desulfurizer front end how continuous and steady operation the problem of annoying enterprise always.This problem
Mainly since coke oven flue gas temperature is relatively low, generally at 300 DEG C hereinafter, select SCR denitration technique when, economically, one
As select low temperature catalyst.Since there are SO in flue gas2, under the action of SCR catalyst, part SO2SO can be converted into3.?
In 180~230 DEG C of sections, ammonia and SO3Reaction easily generates ammonium hydrogen sulfate.Ammonium hydrogen sulfate easily deliquesces, melting temperature 147
DEG C, boiling point is 350 DEG C.The substance is very sticky and is difficult to clean off, and is adhered to catalyst surface, can seriously affect catalyst use
Efficiency.
Rotary spraying technique Na methods desulfurization (the SDA)+middle low-temperature selective catalytic reduction denitration in Baosteel Zhanjiang and Golconda base
(SCR) processing technology routine；The O in Jing Dezhen and Tangshan Huifeng Coking Company coke oven flue gas3Oxidation, NH3Method flue gas desulfurization and denitrification one
Body process route；Inner Mongol Baogang celebrates Central China low-temperature selective catalytic reduction denitration (SCR)+NH3Wet desulfurizing process route
Deng.Trial operation is passed through in exploration in these engineerings, the problems such as purification efficiency is unstable and chimney is hot standby occurs, especially first
Desulfurization, then when carrying out SCR denitration, since sweetening process requires flue-gas temperature relatively low, denitrification process requires flue-gas temperature higher, leads
Cause flue gas to cool, the processes such as heat temperature raising repeatedly, in order to solve first desulfurization again denitration when need to be cooled down to flue gas,
The problem of big caused equipment investment, high energy consumption of heating up, there is an urgent need for develop the desulfurization technology under higher flue-gas temperature.
In conclusion coke oven flue gas desulfurizing and denitrifying process is primarily present following technical problem：
(1) existing coke oven flue gas SDA+SCR desulfurizing and denitrifying process, desulfurizing byproduct are solid-state castoff, can not be carried out
Recycling causes secondary pollution to environment；
(2) existing coke oven flue gas SDA+SCR desulfurizing and denitrifying process, sweetening process are semidry method, and system jams are frequent, fortune
Row stability is poor；
(3) existing coke oven flue gas charcoal base catalytic desulfurization combination S CR denitrating techniques, although desulfurizing byproduct is the dilute of low concentration
Sulfuric acid, amounts of sulphur contaminants has carried out resource utilization utilization, but its utility value is low, need to further concentrate or with concentrated sulfuric acid mixture.
For the technique in denitration, flue gas heating high energy consumption, causing desulphurization denitration to be invested, big, operating cost is high simultaneously.
Invention content
In order to solve the above technical problems, the invention discloses it is a kind of can amounts of sulphur contaminants in effective recycling coke oven flue gas
Coke oven flue gas electromigration desulfurization sulphur technique.
To achieve the above object, the invention discloses a kind of coke oven flue gas electromigration desulfurization sulphur techniques, including come from
Coke oven horizontal flue contains SO2Enter sulfur dioxide electromigration membrane separator with the coke oven flue gas of NOx and passes through electromigration
It is isolated to be rich in SO2Gas and de- SO2Flue gas afterwards, the de- SO2Flue gas, which enters, afterwards is sent into SCR after heat temperature raising in heater
Denitration is completed in Benitration reactor, the flue gas after denitration is sent into outside chimney after waste heat recovery and is arranged；
It is described to be rich in SO2Gas is rich in H with from hydrogen sulfide Analytic Tower2S gases are sent into the burning zone of claus oven together
Reaction generates the Claus tail gases of sulfur-bearing steam, and the Claus tail gases of the sulfur-bearing steam enter sulfur condenser and isolate liquid sulfur
Claus tail gases after sulphur and cooling, the Claus tail gases part after the cooling enter the tail gas cooling section warp of claus oven
Enter hydrogen sulfide Analytic Tower after heat exchange heating as air lift air source and heat source, another part moves after dedusting into sulfur dioxide electricity
Carrier gas of the membrane separator as coke oven flue gas electromigration desulfurization is moved, remainder is incorporated to coal oven dithio-gas pipe network.
Further, Claus tail gases are used to remove Crouse's tail through electrical tar precipitator after cooling is completed in sulfur condenser
Tar, sulphur in gas.
Preferably, the electrical tar precipitator is electrostatic precipitator.
Still further, also supplementing coal gas and air for improving heat of reaction, burning to the burning zone of claus oven
The reaction temperature of section is 1300 DEG C.
Further, separation SO is placed in the sulfur dioxide electromigration membrane separator2The membrane material of gas, it is described
Temperature tolerance >=400 DEG C of membrane material or≤200 DEG C；
When temperature tolerance≤200 DEG C of membrane material, contain SO from coke oven horizontal flue2Coke oven flue gas with NOx is through
One waste heat boiler enters after recycling heat in sulfur dioxide electromigration membrane separator；
When temperature tolerance >=400 DEG C of membrane material, contain SO from coke oven horizontal flue2It is direct with the coke oven flue gas of NOx
Into in sulfur dioxide electromigration membrane separator.
Further, the de- SO2Heated device heat temperature raising again after gas heat exchange in flue gas and heat exchanger afterwards
Afterwards be sent into SCR denitration reactor, the flue gas after denitration enter in heat exchanger as with de- SO2The gas of flue gas heat exchange afterwards.
Further, the flue gas after the denitration is sent into outside chimney after the second waste heat boiler waste heat recovery and is arranged.
The beneficial effects are mainly as follows following aspects：
1, the amounts of sulphur contaminants that the technique that the present invention designs is isolated from coke oven flue gas is rich in SO2Gas, in conjunction with coke
The H of chemical industry sequence coal gas removing2S gases generate the sulfur product of high added value in claus oven, have effectively recycled coke
Amounts of sulphur contaminants in kiln gas；
2, the sulfur dioxide electromigration membrane separator Acclimation temperature range in design technology of the present invention is wide, and coke oven flue gas is not required to
The UF membrane that amounts of sulphur contaminants is carried out in sulfur dioxide electromigration membrane separator, sweetening process can be directly entered by making any temperature adjustment
Middle smoke temperature drop is small, saves follow-up denitrification process flue gas energy consumption, reduces coke oven flue gas desulphurization denitration cost；
3, SO in the sulfur dioxide electromigration membrane separator separation removal coke oven flue gas in design technology of the present invention2, without solid
Useless and waste liquid generates, and sweetening process is not necessarily to any desulfurizing agent, and desulphurization cost is low, technology controlling and process simple operations are convenient, desulfuration efficiency
Up to 90% or more, while electromigration desulfurization, the part NOx in flue gas, 40% or more denitration efficiency can be also removed.
4, the technique that the present invention designs desorbs the gas of air lift using part Claus tail gases as rich solution after coke oven gas desulfurization
Source, the effective recycling waste heat of the part Claus tail gases, with original system using steam as desorption air source compared with, reduce
Coking wastewater yield, improves H2The rate of recovery of S (contains SO in tail gas2And CO2, the pH value of both gases in water is remote
Less than H2S pH value soluble in water, in air lift, both gases reduce H after being dissolved in water2The solubility of S in water improves
Desorption effect).
Description of the drawings
Fig. 1 is the process flow chart of coke oven flue gas electromigration desulfurization sulphur of the present invention；
Fig. 2 is the process flow chart of coke oven flue gas electromigration desulfurization sulphur of the present invention；
Wherein, each part numbers in Fig. 1 and Fig. 2 are as follows：
Coke oven 100 is (wherein：Coke oven flue gas export 110), the first waste heat boiler 100a；
Sulfur dioxide electromigration membrane separator 200 is (wherein：First gas inlet 210, the first exhanst gas outlet 220, carrier gas enter
Mouthfuls 230, carrier gas outlet 240), heater 200a, heat exchanger 200b (the second gas inlet 200b-1, the second exhanst gas outlet 200b-
2, third gas inlet 200b-3, third exhanst gas outlet 200b-4)；
Hydrogen sulphide disposal unit 300 is (wherein：Hydrogen sulfide Analytic Tower 310 is (wherein：Hydrogen sulfide gas exports the 311, first tail
Gas import 312), hydrogen sulfide absorption tower 320)；
Claus oven 400 is (wherein：Burning zone 410, Vaporizing cooling section 420, tail gas cooling section 430 are (wherein：Recycle gram labor
This inlet exhaust gas 440, the outlet of cycle Claus tail gases are 450))；
Sulfur condenser 500, electrical tar precipitator 500a；
SCR denitration reactor 600, the second waste heat boiler 600a；
Coke oven horizontal flue 700 (coke oven combustion chamber outlet section horizontal flue 700a, chimney entrance horizontal flue 700b,
Regulating valve 700c), chimney 700d.
Specific implementation mode
The invention discloses a kind of coke oven flue gas electromigration desulfurization sulphur techniques, as depicted in figs. 1 and 2, including come from
Coke oven horizontal flue 700 contains SO2Enter sulfur dioxide electromigration membrane separator 200 with the coke oven flue gas of NOx to move by electricity
Shifting effect detaches to be rich in SO2Gas and de- SO2Flue gas afterwards, the de- SO2Flue gas enters in heater 200a after heat temperature raising afterwards
It is sent into SCR denitration reactor 600 and completes denitration, the flue gas after denitration is sent into outside chimney 700d after waste heat recovery and is arranged.
Wherein, separation SO is placed in sulfur dioxide electromigration membrane separator 200 of the invention2The membrane material of gas, institute
State membrane material temperature tolerance >=400 DEG C or≤200 DEG C；
As shown in Figure 1, when temperature tolerance≤200 DEG C of membrane material, contain SO from coke oven horizontal flue 7002With NOx's
Coke oven flue gas enters after the first waste heat boiler 100a recycling heats in sulfur dioxide electromigration membrane separator 200；
As shown in Fig. 2, when temperature tolerance >=400 DEG C of membrane material, contain SO from coke oven horizontal flue 7002With NOx's
Coke oven flue gas is directly entered in sulfur dioxide electromigration membrane separator 200.
In addition, described be rich in SO2Gas and being rich in the hydrogen sulfide Analytic Tower 310 of hydrogen sulphide disposal unit 300
H2S gases are sent into reaction in the burning zone 410 of claus oven 400 and generate sulphur steam, the also burning to claus oven 400 together
Coal gas and air of 410 supplement of section for improving heat of reaction, the reaction temperature of burning zone 410 is 1300 DEG C or so, H2S gas
Body, SO2Gas, coal gas and air obtain sulphur under the effect of the catalyst；Remainder be Claus tail gases, the sulphur steam and
Claus tail gases enter sulfur condenser 500 and isolate Claus tail gases after liquid-state sulfur and cooling, it is preferred that in sulfur condenser
Claus tail gases are used to remove Claus tail gases through electrical tar precipitator 500a (preferably electrostatic precipitator) after completing cooling in 500
Middle tar, sulphur, later, a part cooling after Claus tail gases enter claus oven 400 tail gas cooling section 430 it is heated after
H is desorbed into being used as in hydrogen sulfide Analytic Tower 3102The supplement air source and heat source of S gases, a part cooling after Claus tail gases into
Enter in sulfur dioxide electromigration membrane separator 200 as rich in SO2The carrier gas of gas, Claus tail gases after some cooling
It is sent into raw coke oven gas pipeline.
Preferably, the hydrogen sulphide disposal unit 300 includes hydrogen sulfide Analytic Tower 310, hydrogen sulfide absorption tower 320, described
It is loaded with absorbing liquid in hydrogen sulfide absorption tower 320, absorbs the saturated solution after hydrogen sulfide and flows into hydrogen sulfide Analytic Tower 310, one
Hydrogen sulfide gas is precipitated again under the action of fixed temperature and other gases.
Preferably, the claus oven 400 include burning zone 410, Vaporizing cooling section 420 and tail gas cooling section 430, also to
Cooling soft water is supplemented in Vaporizing cooling section 420.
In order to preferably explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
Present disclosure is not limited solely to following embodiment.
Wherein, for 2 × 6 meters of coke-oven plant of embodiment of the present invention coke oven, former coke oven flue gas amount about 250000Nm3/ h, respectively
The coke oven flue gas that combustion chamber comes out respectively enter machine, burnt both sides divide flue to converge after enter the horizontal flue of coke oven.
Embodiment 1
The coke oven flue gas along coke oven 100 is set to export as shown in Figure 1, adjusting the regulating valve 700c on coke oven horizontal flue 700
110 discharges contain SO2Coke oven flue gas with NOx is along coke oven combustion chamber outlet section horizontal flue 700a, sulfur dioxide electromigration
First gas inlet 210 of membrane separator 200 enters in sulfur dioxide electromigration membrane separator 200, titanium dioxide in the present embodiment
The separation SO placed in sulphur electromigration membrane separator 2002Temperature tolerance≤200 DEG C of the membrane material of gas, thus it is preferential using through the
It is entered back into sulfur dioxide electromigration membrane separator 200 after one waste heat boiler 100a recycling heats, the major part in coke oven flue gas
SO2Gas obtains being rich in SO into the other side of seperation film under electromigration2Gas should be rich in SO2Gas is along titanium dioxide
Under the action of Claus tail gases are as carrier gas after the partial warm down that the carrier gas inlet 230 of sulphur electromigration membrane separator 200 flows into, stream
Go out the carrier gas outlet 240 of sulfur dioxide electromigration membrane separator 200, and goes out with the hydrogen sulfide gas along hydrogen sulfide Analytic Tower 310
311 discharge of mouth is rich in H2S gases are sent into the burning zone 410 of claus oven 400 together, and the claus oven 400 includes burning
Section 410, Vaporizing cooling section 420 and tail gas cooling section 430 are additionally provided with cycle Claus tail gases import on tail gas cooling section 430
440 export 450 with cycle Claus tail gases, also coal gas and air for improving heat of reaction are supplemented to burning zone 410, to vapour
Change and supplements cooling soft water in cooling section 420；It is rich in hydrogen sulfide gas, sulfur dioxide gas and edge into claus oven 400
The coal gas of the air inlet supplement of claus oven 400, that air carries out Crouse under the action of 1300 DEG C of temperature and catalyst is anti-
High temperature sulphur steam and Claus tail gases should be obtained, the high temperature sulphur steam and Claus tail gases enter sulfur condenser 500 and divide
Claus tail gases after separating out liquid-state sulfur and cooling down, Claus tail gases are along cycle Claus tail gases import 440 after part cooling
Into tail gas cooling section 430 after heat exchange heats up after again along 450 outflow claus ovens 400 of cycle Claus tail gases outlet, and edge
First inlet exhaust gas 312 of 310 bottom end of hydrogen sulfide Analytic Tower setting enters in hydrogen sulfide Analytic Tower 310 as desorption H2S gases
Supplement air source and heat source；Claus tail gases are burnt in Claus tail gases for removing through electrical tar precipitator 500a after part cooling
It is admitted to after oil, sulphur in sulfur dioxide electromigration membrane separator 200 as rich in SO2The carrier gas of gas, some drop
(process flow chart of the present embodiment does not embody gas trend, but includes this in Claus tail gases feeding raw coke oven gas pipeline after temperature
Part).
Fig. 1 is recombined it is found that being additionally provided on sulfur dioxide electromigration membrane separator 200 for de- SO to be discharged2Cigarette afterwards
First exhanst gas outlet 220 of gas, the de- SO2Second gas inlet 200b-1 of the flue gas on heat exchanger 200b enters afterwards,
It is arranged along the second exhanst gas outlet 200b-2 after carrying out heat exchange with the flue gas after the denitration of entrance heat exchanger 200b in heat exchanger 200b
Go out to enter in heater 200a and be sent into SCR denitration reactor 600 after continuation heat temperature raising, is also mended into SCR denitration reactor 600
Ammonia is filled, nitrogen oxides occurs SCR under denitrating catalyst effect with ammonia and reacts, and the flue gas after the high temperature denitration is along third cigarette
Gas import 200b-3 enter in heat exchanger 200b as with de- SO2The gas of flue gas heat exchange afterwards, and along third exhanst gas outlet
After 200b-4 discharges, it is sent into outside chimney 700d and arranges along chimney entrance horizontal flue 700b.
By the implementation of above scheme, SO in coke oven flue gas2Drop to 50mg/Nm3, NOx drop to 100mg/Nm3, in flue gas
SO2Recovery utilization rate reaches 95%.
Embodiment 2
The coke oven flue gas along coke oven 100 is set to export as shown in Fig. 2, adjusting the regulating valve 700c on coke oven horizontal flue 700
110 discharges contain SO2Coke oven flue gas with NOx is along coke oven combustion chamber outlet section horizontal flue 700a, sulfur dioxide electromigration
First gas inlet 210 of membrane separator 200 enters in sulfur dioxide electromigration membrane separator 200, titanium dioxide in the present embodiment
The separation SO placed in sulphur electromigration membrane separator 2002Temperature tolerance >=400 DEG C of the membrane material of gas, therefore preferential use comes from
Coke oven horizontal flue 700 contains SO2It is directly entered in sulfur dioxide electromigration membrane separator 200 with the coke oven flue gas of NOx, it is burnt
Most of SO in kiln gas2Gas obtains being rich in SO into the other side of seperation film under electromigration2Gas, this is rich in
SO2Gas after the partial warm down that the carrier gas inlet 230 of sulfur dioxide electromigration membrane separator 200 flows into Claus tail gases make
Under the action of carrier gas, the carrier gas outlet 240 of outflow sulfur dioxide electromigration membrane separator 200, and with along hydrogen sulfide Analytic Tower
310 311 discharge of hydrogen sulfide gas outlet is rich in H2S gases are sent into the burning zone 410 of claus oven 400 together, described gram
Louth stove 400 includes burning zone 410, Vaporizing cooling section 420 and tail gas cooling section 430, is additionally provided with and follows on tail gas cooling section 430
Ring Claus tail gases import 440 and cycle Claus tail gases outlet 450, are also supplemented to burning zone 410 for improving heat of reaction
Coal gas and air, cooling soft water is supplemented into Vaporizing cooling section 420；Into in claus oven 400 rich in hydrogen sulfide gas,
Coal gas that sulfur dioxide gas is supplemented with the air inlet along claus oven 400, air is in 1300 DEG C of temperature and the work of catalyst
Carry out claus reaction under and obtain high temperature sulphur steam and Claus tail gases, the high temperature sulphur steam and Claus tail gases into
Enter sulfur condenser 500 and isolate Claus tail gases after liquid-state sulfur and cooling, Claus tail gases are along cycle gram after part cooling
It is heated rear again along 450 outflow claus ovens of cycle Claus tail gases outlet that Louth inlet exhaust gas 440 enters tail gas cooling section 430
400, and enter in hydrogen sulfide Analytic Tower 310 as desorption along the first inlet exhaust gas 312 of 310 bottom end of hydrogen sulfide Analytic Tower setting
H2The supplement air source and heat source of S gases；Claus tail gases are used to remove Crouse through electrical tar precipitator 500a after part cooling
It is admitted to after tar, sulphur in tail gas in sulfur dioxide electromigration membrane separator 200 as rich in SO2The carrier gas of gas, also
A part cooling after Claus tail gases be sent into raw coke oven gas pipeline in (process flow chart of the present embodiment do not embody the gas trend,
But including this part).
Fig. 2 is recombined it is found that being additionally provided on sulfur dioxide electromigration membrane separator 200 for de- SO to be discharged2Cigarette afterwards
First exhanst gas outlet 220 of gas, the de- SO2Flue gas is directly entered in heater 200a and is sent into SCR after completion heat temperature raising afterwards
Benitration reactor 600 also supplements ammonia into SCR denitration reactor 600, and nitrogen oxides is with ammonia under denitrating catalyst effect
SCR reactions occur, the flue gas after the high temperature denitration is after the second waste heat boiler 600a recycling heats, along the horizontal cigarette of chimney entrance
Road 700b is sent into outside chimney 700d and arranges.
Above example is only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodiment
Outside, the present invention also has other embodiment.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present invention
It is required that protection domain.
Claims (6)
1. a kind of coke oven flue gas electromigration desulfurization sulphur technique, it is characterised in that：Including coming from coke oven horizontal flue (700)
Contain SO2Enter sulfur dioxide electromigration membrane separator (200) with the coke oven flue gas of NOx and passes through the isolated richness of electromigration
Containing SO2Gas and de- SO2Flue gas afterwards, the de- SO2Flue gas enters in heater (200a) afterwards is sent into SCR denitration after heat temperature raising
Denitration is completed in reactor (600), the flue gas after denitration is sent into chimney (700d) after waste heat recovery and is arranged outside；
It is described to be rich in SO2Gas is rich in H with from hydrogen sulfide Analytic Tower (310)2S gases are sent into claus oven (400) together
Burning zone (410) reaction generates the Claus tail gases of sulfur-bearing steam, and the Claus tail gases of the sulfur-bearing steam enter sulfur condenser
(500) Claus tail gases after liquid-state sulfur and cooling are isolated, the Claus tail gases part after the cooling enters gram labor
The tail gas cooling section (430) of this stove (400) enters hydrogen sulfide Analytic Tower (310) after heat exchange heats up and is used as air lift air source and heat
Source, another part enter load of the sulfur dioxide electromigration membrane separator (200) as coke oven flue gas electromigration desulfurization after dedusting
Gas, remainder are incorporated to coal oven dithio-gas pipe network.
2. coke oven flue gas electromigration desulfurization sulphur technique according to claim 1, it is characterised in that：In sulfur condenser
(500) Claus tail gases are used to remove tar in Claus tail gases, sulphur through electrical tar precipitator (500a) after completing cooling in.
3. coke oven flue gas electromigration desulfurization sulphur technique according to claim 1, it is characterised in that：Also to claus oven
(400) burning zone (410) supplements the coal gas and air for improving heat of reaction, and the reaction temperature of burning zone (410) is
1300℃。
4. according to any one of claims 1 to 3 coke oven flue gas electromigration desulfurization sulphur technique, it is characterised in that：
Separation SO is placed in the sulfur dioxide electromigration membrane separator (200)2The membrane material of gas, the temperature tolerance of the membrane material
>=400 DEG C or≤200 DEG C；
When temperature tolerance≤200 DEG C of membrane material, contain SO from coke oven horizontal flue (700)2Coke oven flue gas with NOx is through
One waste heat boiler (100a) enters after recycling heat in sulfur dioxide electromigration membrane separator (200)；
When temperature tolerance >=400 DEG C of membrane material, contain SO from coke oven horizontal flue (700)2It is direct with the coke oven flue gas of NOx
Into in sulfur dioxide electromigration membrane separator (200).
5. coke oven flue gas electromigration desulfurization sulphur technique according to claim 4, it is characterised in that：The de- SO2Flue gas afterwards
Be sent into SCR denitration reactor after the gas heat exchange in heat exchanger (200b) after heated device (200a) heat temperature raising again
(600), the flue gas after denitration enter in heat exchanger (200b) as with de- SO2The gas of flue gas heat exchange afterwards.
6. coke oven flue gas electromigration desulfurization sulphur technique according to claim 4, it is characterised in that：Cigarette after the denitration
Gas is sent into chimney (700d) after the second waste heat boiler (600a) waste heat recovery and is arranged outside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810556138.8A CN108786441B (en) | 2018-05-31 | 2018-05-31 | Sulfur preparation process by electromigration desulfurization of coke oven flue gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810556138.8A CN108786441B (en) | 2018-05-31 | 2018-05-31 | Sulfur preparation process by electromigration desulfurization of coke oven flue gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108786441A true CN108786441A (en) | 2018-11-13 |
| CN108786441B CN108786441B (en) | 2021-03-19 |
Family
ID=64090005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810556138.8A Active CN108786441B (en) | 2018-05-31 | 2018-05-31 | Sulfur preparation process by electromigration desulfurization of coke oven flue gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108786441B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534300A (en) * | 2018-12-27 | 2019-03-29 | 陈萌 | A kind of preprocess method of flue gas during smelting |
| CN109573958A (en) * | 2018-12-27 | 2019-04-05 | 陈萌 | A kind of resource utilization method of flue gas during smelting |
| US20220227625A1 (en) * | 2019-05-03 | 2022-07-21 | Haldor Topsøe A/S | Method for production of elemental sulfur and sulfuric acid |
| CN116477580A (en) * | 2023-04-26 | 2023-07-25 | 福州大学 | A process and system for recyclable hydrogen sulfide adsorbent to decompose gas to sulfur |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2745099B2 (en) * | 1993-03-23 | 1998-04-28 | 三菱化工機株式会社 | Klaus tail gas treatment equipment |
| CN102198363A (en) * | 2010-03-25 | 2011-09-28 | 中国石油化工股份有限公司 | Film based recovery method of sulfur in flue gas |
| CN104962333A (en) * | 2015-05-29 | 2015-10-07 | 西安建筑科技大学 | Membrane separation biogas biological desulfurization method and device |
| CN107875838A (en) * | 2017-12-15 | 2018-04-06 | 马鞍山钢铁股份有限公司 | With the production technology and processing system of compound claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour |
-
2018
- 2018-05-31 CN CN201810556138.8A patent/CN108786441B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2745099B2 (en) * | 1993-03-23 | 1998-04-28 | 三菱化工機株式会社 | Klaus tail gas treatment equipment |
| CN102198363A (en) * | 2010-03-25 | 2011-09-28 | 中国石油化工股份有限公司 | Film based recovery method of sulfur in flue gas |
| CN104962333A (en) * | 2015-05-29 | 2015-10-07 | 西安建筑科技大学 | Membrane separation biogas biological desulfurization method and device |
| CN107875838A (en) * | 2017-12-15 | 2018-04-06 | 马鞍山钢铁股份有限公司 | With the production technology and processing system of compound claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour |
Non-Patent Citations (3)
| Title |
|---|
| 大连理工大学化工原理教研室: "《化工原理课程设计》", 31 July 1994 * |
| 李培元等: "《发电厂水处理及水质控制》", 30 November 2011 * |
| 王祖武等: "放电电场对SO2气相传质过程的影响", 《中国电机工程学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534300A (en) * | 2018-12-27 | 2019-03-29 | 陈萌 | A kind of preprocess method of flue gas during smelting |
| CN109573958A (en) * | 2018-12-27 | 2019-04-05 | 陈萌 | A kind of resource utilization method of flue gas during smelting |
| US20220227625A1 (en) * | 2019-05-03 | 2022-07-21 | Haldor Topsøe A/S | Method for production of elemental sulfur and sulfuric acid |
| CN116477580A (en) * | 2023-04-26 | 2023-07-25 | 福州大学 | A process and system for recyclable hydrogen sulfide adsorbent to decompose gas to sulfur |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108786441B (en) | 2021-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7075910B2 (en) | Acid gas treatment | |
| CN104689679B (en) | Desulfurization and denitrification process for coke oven flue gas | |
| CN108654362B (en) | Coking waste gas purification system | |
| CN108786441A (en) | Coke oven flue gas electromigration desulfurization sulphur technique | |
| CN103170223B (en) | The eddy flow intensifying method of Clause method sulfur production tail gas clean-up and device | |
| CN108704474B (en) | Coke oven flue gas and Claus tail gas combined treatment process | |
| US5120517A (en) | Process for the removal of sulfur oxides and nitrogen oxides from flue gas | |
| CN106430111A (en) | Method for preparing sulfur by recycling sulfur dioxide from flue gas | |
| CN108975285A (en) | A kind of wet process sulphuric acid plant and a kind of method of wet desulphurization | |
| CN108176194A (en) | A kind of processing unit and processing method containing sulphur simple substance and compound tail gas | |
| CN108355463B (en) | A kind of desulfurization method and device of sulfur tail gas | |
| CN101193690A (en) | Treatment of fuel gas | |
| CN107875838A (en) | With the production technology and processing system of compound claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour | |
| CN111470476A (en) | Method for recycling and recovering sulfur from regenerated sulfur-containing tail gas subjected to active coke dry method flue gas treatment | |
| CN108654363A (en) | Couple waste heat of coke-oven flue gas and amounts of sulphur contaminants acid-making process | |
| CN113264508B (en) | Sulfur recovery method and device | |
| CN208082173U (en) | The processing system of activated coke method coke oven flue gas desulphurization denitration acid vapour is handled with system for preparing sulfuric acid | |
| CN216726614U (en) | Desulfurization regeneration tail gas processing system | |
| CN216614549U (en) | Blast furnace gas desulfurization and dechlorination purification device | |
| CN113385004B (en) | Desulfurization method and device for sulfur production tail gas | |
| CN115285941A (en) | A kind of method for producing sulfur by low-temperature catalytic direct reduction of SO2 in flue gas | |
| CN104556147A (en) | Process for preparing SCR reducing agent from coking residual ammonia wastewater as raw material | |
| CN107890755A (en) | With the production technology and processing system of system for preparing sulfuric acid processing activated coke method coke oven flue gas desulphurization denitration acid vapour | |
| CN216630292U (en) | Coking industry chemical production area VOCs processing system | |
| CN107875839A (en) | With the production technology and processing system of claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |