CN107875839A - With the production technology and processing system of claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour - Google Patents

With the production technology and processing system of claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour Download PDF

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Publication number
CN107875839A
CN107875839A CN201711349708.8A CN201711349708A CN107875839A CN 107875839 A CN107875839 A CN 107875839A CN 201711349708 A CN201711349708 A CN 201711349708A CN 107875839 A CN107875839 A CN 107875839A
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China
Prior art keywords
coke
oven
flue gas
vapour
sour
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CN201711349708.8A
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Inventor
王永林
邱全山
汪开保
郑德�
熊燕
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Maanshan Iron and Steel Co Ltd
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Maanshan Iron and Steel Co Ltd
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Priority to CN201711349708.8A priority Critical patent/CN107875839A/en
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    • 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
    • B01D53/81—Solid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/60—Simultaneously removing sulfur oxides and 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • 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
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • 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

Abstract

The invention discloses a kind of production technology and processing system that activated coke method coke oven flue gas desulphurization denitration acid vapour is handled with claus oven, a kind of claus oven process unit using the original processing coke-stove gas acid ammonia gas production sulphur in coke-oven plant is provided to handle the process of sour vapour caused by activated coke method coke oven flue gas desulphurization denitration, the original appliance arrangement of this process makes full use, only need the conveying equipment and cleaner of sour vapour caused by increase activated coke method coke oven flue gas desulphurization denitration, do not increase other energy and equipment additionally, pollutant in sour vapour caused by the sour ammonia gas of coke-stove gas and activated coke method coke oven flue gas desulphurization denitration can be converted into the chemical products sulphur of high added value, technique advantages of simple, investment cost is low, and without waste water, the waste discharges such as waste residue, with unexpected technique effect.

Description

With the production work of claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour Skill and processing system
Technical field
The invention belongs to coal chemical industry and petrochemical industry flue gases purification field, and in particular to handle and live with claus oven The production technology and processing system of property Jiao's method coke oven flue gas desulphurization denitration acid vapour.
Background technology
Coke oven is one of equipment that atmosphere pollution most serious is caused in metallurgy industry, and the pollutant component of coke oven discharge is answered It is miscellaneous, contain nitrogen oxides (NOx), sulfur dioxide, carbon monoxide, carbon dioxide, hydrogen sulfide, hydrogen cyanide, residual ammonia, phenol and coal Dirt, tar etc..From 1 day January in 2015, the pollutant emission of coke oven flue gas performs GB16171-2012《Coking chemistry industry is dirty Contaminate thing discharge standard》Regulation, to the SO of coke oven flue gas2And NOXDischarge propose strict requirements.Exploitation both at home and abroad at present Flue gas desulfurization and denitrification technology it is a lot, wherein activated coke method coke oven flue gas desulphurization denitration handling process is widely used.
Activated coke method (being also known as activated carbon method) is the absorption property using activated coke itself, to SO2And NOXCarry out physics And chemisorbed, so as to reach a kind of method of desulfurization off sulfide effect.During for flue gases of cock oven desulphurization denitration, using waste heat Heat energy in boiler recovered flue gas first, flue gas are passed through after being cooled in activated coke adsorptive purifier.At its desulphurization denitration The principle of science and engineering skill is：In the presence of catalyst, in desulphurization denitration purifying column, the SO in flue gas2、O2、H2O molecules are lived Property burnt (desulfurizing agent) catch and generate sulfuric acid, the NO in flue gasXIn NH3Reduction under react and generate the N of nontoxic pollution-free2With H2O, coke oven flue gas are purified qualified discharge.The activated coke (desulfurizing agent) of sulfuric acid has been adsorbed in regenerator in certain temperature Lower desorption and regeneration, i.e., sulfuric acid and C reaction generations SO in regenerator2And H2O and CO2, current technique is by containing SO2Acidity Gas delivers to sulphur ammonium system production sulphur ammonium, and the activated coke (desulfurizing agent) after regeneration recycles in purifying.Specific technique is shown in Fig. 1 activated coke method coke oven flue gas desulfurizing and denitrifying process schematic flow sheets.
Contain SO in existing activated coke method coke oven flue gas desulfurizing and denitrifying process2Sour gas to sulphur ammonium system production sulphur ammonium This technique, under conditions of no oxidation, SO2And NH3Generate ammonium sulfite (NH4)2SO3, rather than generation ammonium sulfate (NH4)2SO4, ammonium sulfate product quality can be so influenceed, its Process configuration is nor quite reasonable.
The content of the invention
It is an object of the present invention to provide a kind of Ke Lao using the original processing coke-stove gas acid ammonia gas production sulphur in coke-oven plant This furnaceman's process and equipment handles the process of sour vapour caused by activated coke method coke oven flue gas desulphurization denitration, this process makes full use Original appliance arrangement, it is only necessary to increase the conveying equipment of sour vapour and dedusting caused by activated coke method coke oven flue gas desulphurization denitration and set It is standby, do not increase other energy and equipment additionally, you can take off the sour ammonia gas of coke-stove gas and activated coke method coke oven flue gas desulfurization Pollutant in sour vapour caused by nitre is converted into chemical products-sulphur of high added value, and technique advantages of simple, investment cost is low, And without waste discharges such as waste water, waste residues, there is unexpected technique effect.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of production technology that activated coke method coke oven flue gas desulphurization denitration acid vapour is handled with claus oven, its feature exist In：
(1) conveying of a sour vapour is increased on the sour steam pipe road of activated coke method coke oven flue gas desulphurization denitration regenerator outlet Equipment, activated coke method coke oven flue gas desulphurization denitration regenerated acid vapour is delivered to next device；
(2) after conveying equipment increase a dust removal by filtration dehydration equipment, be filtered to remove regenerated acid vapour entrainment dust and Moisture；
(3) claus oven system is connected after dust removal by filtration dehydration equipment, the system is washed to handle coke oven gas desulfurization The supporting deacidifion unit of ammonia contains H2S gases produce original process unit of sulphur, wherein, the regenerated acid vapour of step (2) contains There is SO2, claus oven system can automatically adjust combustion air amount by aerobic analyzer, while coke oven gas desulfurization is washed into ammonia and matched somebody with somebody The deacidifion unit of set contains H2The SO that S gases and the outlet of activated coke method coke oven flue gas desulphurization denitration regenerator contain2Sour vapour generation Sulphur；
(4) gas piping is inhaled before connecting primary cooler after claus oven system, will be arranged outside the tail gas of step (3).
Preferably, the coke oven gas desulfurization of step (3), which is washed the supporting deacidifion unit of ammonia and removed, contains H2Outside S, it can also contain There is a small amount of NH3, HCN and CO2Etc. multiple gases.
It is furthermore preferred that the sour vapour of the activated coke method coke oven flue gas desulphurization denitration regenerator outlet of step (1) removes and contains SO2 Outside, CO can also be contained2、H2O、N2Etc. multiple gases.
It is furthermore preferred that the sour vapour of activated coke method coke oven flue gas desulphurization denitration regenerator outlet is by desulphurization denitration purifying column Purification, and it is as shown in Figure 2 in the activated coke method coke oven flue gas desulphurization denitration acid vapour of regenerator desorption and regeneration, its technological process.
Claus oven washes the supporting deacidifion unit of ammonia handling coke oven gas desulfurization and contains H2S gases production sulphur Original process unit, its reaction principle are：The combustion air amount of claus oven is controlled by aerobic analyzer, will about sour ammonia gas In 1/3 H2S burning generations SO2, the SO of generation2With remaining H2S reaction generation sulphur.Reaction equation is：
H2S combustion reactions：H2S+3/2O2→SO2+H2O
Claus reaction：2H2S+SO2→3/X SX+2H2O
Whole reaction：3H2S+3/2O2→3/X SX+3H2O
Wash the supporting deacidifion unit of ammonia when coke oven gas desulfurization and remove and contain H2Outside S, a small amount of NH can also be contained3, HCN and CO2During etc. multiple gases, the NH in sour ammonia vapour3And HCN catalytic pyrolysis under claus oven high temperature and catalyst action is H2、N2 And CO.
The purpose of the present invention is the claus oven technique with the original processing coke-stove gas acid ammonia gas production sulphur in coke-oven plant Device handles sour vapour caused by activated coke method coke oven flue gas desulphurization denitration.
The composition of sour vapour of activated coke method coke oven flue gas desulphurization denitration regenerator outlet is：SO2Content 5%~30%, contains Dirt 2g/Nm3Left and right, water content 10%~40%, remaining gas are nitrogen and carbon dioxide, sour vapour for temperature 150 DEG C~350 ℃。
The SO of the sour vapour of activated coke method coke oven flue gas desulphurization denitration regenerator outlet2Although total amount is well below claus oven Handle H in deacidifion acid ammonia vapour2Meet the SO required for claus reaction during S2Amount, but can by aerobic analyzer from Dynamic regulation combustion air amount, under less combustion air amount effect, while coke oven gas desulfurization is washed into the supporting depickling of ammonia and steamed Ammonia unit contains H2The SO that S gases and the outlet of activated coke method coke oven flue gas desulphurization denitration regenerator contain2Sour vapour generates sulphur.
The invention further relates to a kind of activated coke method coke oven flue gas desulphurization denitration acid vapour processing system, the system includes sour vapour Gas piping is inhaled before conveying equipment, dust removal by filtration dehydration equipment, claus oven, primary cooler, it is characterised in that：The acid gas conveying The sour steam pipe road that equipment exports with activated coke method coke oven flue gas desulphurization denitration regenerator is connected, the outlet of sour vapour conveying equipment again with mistake Filtering dust collecting dehydration equipment is connected, and the outlet of dust removal by filtration equipment is connected with claus oven, and claus oven outlet before primary cooler with inhaling coal Feed channel connects, wherein, claus oven is provided with aerobic analyzer.
Preferably, the sour vapour conveying equipment is air blower.
Preferably, the claus oven is that processing coke oven gas desulfurization washes the supporting deacidifion unit of ammonia and contains H2S vapour Body produces original process unit of sulphur, is by H2S etc. generates sulphur and by a small amount of NH3, HCN be decomposed into N2Deng combustion furnace.
Preferably, it is the suction gas piping before coke oven gas primary-cooling device that gas piping is inhaled before the primary cooler.
Brief description of the drawings
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is activated coke method coke oven flue gas desulfurizing and denitrifying process schematic flow sheet
Fig. 2 is the process flow diagram that claus oven handles activated coke method coke oven flue gas desulphurization denitration acid vapour
In Fig. 2：
1) waste heat utilization equipment of waste heat boiler --- coke oven flue gas；
2) blowdown stack of chimney --- coke oven flue gas；
3) purifying column --- the purifier of coke oven flue gas activated coke method desulphurization denitration；
4) regenerator --- SO in removal activity Jiao2And H2O and CO2Regenerating unit；
5) air blower --- the equipment of conveying regeneration vapour；
6) filtering dedusting dehydration equipment --- purifying regeneration vapour filtering dedusting and dehydration equipment；
7) claus oven --- by H2S etc. generates sulphur and by NH3, HCN be decomposed into N2Deng combustion furnace；
8) gas piping is inhaled before primary cooler --- the suction gas piping before coke oven gas primary-cooling device.
Embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1
As shown in figure 1, Fig. 1 provides activated coke method coke oven flue gas desulfurizing and denitrifying process schematic flow sheet, first, using remaining Heat boiler recovery coke oven flue gas SO2And NOXIn heat energy, flue gas is passed through after being cooled in activated coke adsorption cleaning tower, in desulfurization In denitration purifying column, the SO in flue gas2、O2、H2O molecules are caught by activated coke (desulfurizing agent) and generate sulfuric acid, the NO in flue gasX In NH3Reduction under react and generate the N of nontoxic pollution-free2And H2O, coke oven flue gas are purified qualified discharge.Sulfuric acid is adsorbed Activated coke (desulfurizing agent) desorption and regeneration at a certain temperature, i.e., sulfuric acid and C reaction generations in regenerator in regenerator SO2And H2O and CO2, SO will be contained2Sour gas deliver to sulphur ammonium system production sulphur ammonium, the activated coke (desulfurizing agent) after regeneration is to net Recycled in changing.Because sulphur ammonium system is under conditions of no oxidation, SO2And NH3Generate ammonium sulfite (NH4)2SO3, without It is generation ammonium sulfate (NH4)2SO4, have impact on ammonium sulfate product quality.
Embodiment 2
As shown in Fig. 2 Fig. 2 provides the technological process of claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour Schematic diagram, the difference with embodiment 1 be, the SO of the activated coke method coke oven flue gas desulphurization denitration regenerator of embodiment 1 outlet2And H2O And CO2Regeneration vapour acid steam pipe road be no longer passed through sulphur ammonium system, will on the sour steam pipe road increase a sour vapour conveying equipment, will Activated coke method coke oven flue gas desulphurization denitration regenerated acid vapour is delivered to next device；Increase a dust removal by filtration after conveying equipment to take off Wetting system, the dust and moisture of the entrainment of regenerated acid vapour are filtered to remove, to avoid the dust of sour vapour entrainment from blocking urging for claus oven Agent；Increase a claus oven system after dust removal by filtration dehydration equipment, the system washes ammonia to handle coke oven gas desulfurization Supporting deacidifion unit contains H2S gases produce original process unit of sulphur, because activated coke method coke oven flue gas desulfurization takes off Contain SO in the sour vapour of nitre regenerator outlet2, coke oven gas desulfurization washes the supporting deacidifion unit of ammonia and contains H2S gases, but activity The composition of the sour vapour of burnt method coke oven flue gas desulphurization denitration regenerator outlet is：SO2Content 5%~30%, dust-laden 2g/Nm3Left and right, Water content 10%~40%, remaining gas are nitrogen and carbon dioxide, sour vapour for 150 DEG C~350 DEG C of temperature, activated coke method it is burnt The SO of the sour vapour of kiln gas desulphurization denitration regenerator outlet2Total amount handles H in deacidifion acid ammonia vapour well below claus oven2S When meet SO required for claus reaction2Amount, therefore, can be provided with by claus oven aerobic point of claus oven system Analyzer automatically adjusts combustion air amount, while coke oven gas desulfurization is washed into the supporting deacidifion unit of ammonia and contains H2S gases and The SO that the outlet of activated coke method coke oven flue gas desulphurization denitration regenerator contains2Sour vapour generates sulphur, and the method does not produce the tail gas arranged outside, Caused tail gas is discharged together with Claus tail gases by inhaling gas piping before the latter linked primary cooler of claus oven system.Should The coke oven gas desulfurization of system processing, which is washed the supporting deacidifion unit of ammonia and removed, contains H2Outside S, a small amount of NH can also be contained3, HCN and CO2Etc. multiple gases, can get a desired effect.
Above content is only that affiliated those skilled in the art are to being retouched to examples of the invention and explanation Various modifications may be made or supplement for the specific embodiment stated, and design without departing from the present invention or surmounts the claims and is defined Scope, protection scope of the present invention all should be belonged to.

Claims (8)

  1. A kind of 1. production technology that activated coke method coke oven flue gas desulphurization denitration acid vapour is handled with claus oven, it is characterised in that：
    (1) conveying for increasing a sour vapour on the sour steam pipe road of activated coke method coke oven flue gas desulphurization denitration regenerator outlet is set It is standby, activated coke method coke oven flue gas desulphurization denitration regenerated acid vapour is delivered to next device；
    (2) increase a dust removal by filtration dehydration equipment after conveying equipment, be filtered to remove the dust and moisture of the entrainment of regenerated acid vapour；
    (3) claus oven system is connected after dust removal by filtration dehydration equipment, the system is washed ammonia handling coke oven gas desulfurization and matched somebody with somebody The deacidifion unit of set contains H2S gases produce original process unit of sulphur, wherein, the regenerated acid vapour of step (2) contains SO2, Claus oven system can automatically adjust combustion air amount by aerobic analyzer, while coke oven gas desulfurization is washed into supporting de- of ammonia Sour ammonia still process unit contains H2The SO that S gases and the outlet of activated coke method coke oven flue gas desulphurization denitration regenerator contain2Sour vapour generates sulphur；
    (4) gas piping is inhaled before connecting primary cooler after claus oven system, will be arranged outside the tail gas of step (3).
  2. 2. production technology as claimed in claim 1, it is characterised in that：Coke oven gas desulfurization washes the supporting deacidifion unit of ammonia Except containing H2Outside S, also contain NH3, HCN and CO2。
  3. 3. production technology as claimed in claim 1, it is characterised in that：Activated coke method coke oven flue gas desulphurization denitration regenerator exports Sour vapour except containing SO2Outside, CO is also contained2、H2O、N2。
  4. 4. production technology as claimed in claim 1, it is characterised in that：Taken off with claus oven processing activated coke method coke oven flue gas The technological process of sulphur denitrated acid vapour is as shown in Figure 2.
  5. 5. a kind of activated coke method coke oven flue gas desulphurization denitration acid vapour processing system, the system includes sour vapour conveying equipment, filtering Gas piping is inhaled before dedusting dehydration equipment, claus oven, primary cooler, it is characterised in that：The acid gas conveying equipment and activated coke The sour steam pipe road connection of method coke oven flue gas desulphurization denitration regenerator outlet, sour vapour conveying equipment outlet are set with dust removal by filtration dehydration again Standby connection, the outlet of dust removal by filtration equipment are connected with claus oven, and claus oven outlet is connected with inhaling gas piping before primary cooler, its In, claus oven is provided with aerobic analyzer.
  6. 6. sour vapour processing system as claimed in claim 5, the sour vapour conveying equipment is air blower.
  7. 7. sour vapour processing system as claimed in claim 5, it is supporting that the claus oven for processing coke oven gas desulfurization washes ammonia Deacidifion unit contains H2S gases produce original process unit of sulphur.
  8. 8. sour vapour processing system as claimed in claim 5, inhaled before the primary cooler before gas piping is coke oven gas primary-cooling device Suction gas piping.
CN201711349708.8A 2017-12-15 2017-12-15 With the production technology and processing system of claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour Pending CN107875839A (en)

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Title
曹胜利等, 冶金工业出版社 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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