CN112915777A - Blast furnace gas dechlorination, desulfurization and purification process - Google Patents
Blast furnace gas dechlorination, desulfurization and purification process Download PDFInfo
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- CN112915777A CN112915777A CN201911233736.2A CN201911233736A CN112915777A CN 112915777 A CN112915777 A CN 112915777A CN 201911233736 A CN201911233736 A CN 201911233736A CN 112915777 A CN112915777 A CN 112915777A
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- 238000006477 desulfuration reaction Methods 0.000 title claims description 35
- 230000023556 desulfurization Effects 0.000 title claims description 35
- 238000000746 purification Methods 0.000 title claims description 18
- 238000006298 dechlorination reaction Methods 0.000 title claims description 11
- 239000007789 gas Substances 0.000 claims abstract description 143
- 239000000428 dust Substances 0.000 claims abstract description 48
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 46
- 230000007062 hydrolysis Effects 0.000 claims abstract description 41
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004744 fabric Substances 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 230000005484 gravity Effects 0.000 claims abstract description 16
- 238000010248 power generation Methods 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 34
- 238000010521 absorption reaction Methods 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000003463 adsorbent Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 23
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 230000008929 regeneration Effects 0.000 claims description 18
- 238000011069 regeneration method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 238000005243 fluidization Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052680 mordenite Inorganic materials 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000002918 waste heat Substances 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000007255 decyanation reaction Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 231100000572 poisoning Toxicity 0.000 claims description 2
- 230000000607 poisoning effect Effects 0.000 claims description 2
- 235000018553 tannin Nutrition 0.000 claims description 2
- 229920001864 tannin Polymers 0.000 claims description 2
- 239000001648 tannin Substances 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000382 dechlorinating effect Effects 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 14
- 239000003034 coal gas Substances 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
- B01D50/20—Combinations of devices covered by groups B01D45/00 and B01D46/00
-
- 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
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- 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
- B01D53/54—Nitrogen compounds
-
- 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
- B01D53/68—Halogens or halogen compounds
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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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/104—Oxygen
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Abstract
The invention discloses a blast furnace gas dechlorinating, desulfurizing and purifying process. Firstly, the pipeline between the gravity dust removal and the cloth bag dust removal is used as a deacidification fluidized bed reactor to remove hydrogen chloride and cyanic acid in blast furnace gas, and then the blast furnace gas enters a deoxidation reactor to catalyze and remove O2Then the organic sulfur is hydrolyzed into H in an organic sulfur hydrolysis conversion reactor2S, finally entering a wet method for removingThe sulfur system removes sulfides. The process does not influence the dry dedusting and the residual pressure turbine power generation device to recover the residual pressure and the residual heat for power generation, can efficiently remove chloride, cyanide and sulfide in the blast furnace gas, and has the characteristics of high removal precision, simple flow, small pressure drop and temperature drop, simple equipment, less investment, low operation cost and small occupied area, and the whole technical and economic advantages are very obvious.
Description
Technical Field
The invention relates to a process for dechlorinating, desulfurizing and purifying blast furnace gas, belonging to the field of coal chemical industry.
Background
3500-4000 m blast furnace gas is generated when 1 ton of coke is consumed in the iron making process, and the reasonable and effective utilization of the blast furnace gas has important significance for circular economy, energy conservation and emission reduction. In recent years, with the widespread use of blast furnace gas dry dedusting and residual pressure turbine power generation units (TRTs), the pressure energy and heat energy of blast furnace gas are sufficiently recovered, the enterprise efficiency is improved, and the development of enterprises is promoted, but harmful substances (such as chloride, sulfide, and cyanide) in the gas are not effectively treated, SO that not only pipelines and power generation equipment are corroded, but also SO is emitted in the combustion of the lower section2And HCl causes serious environmental pollution. With the implementation of the ultralow emission standard of atmospheric pollutants in the iron and steel industry, the flue gas SO generated after the combustion of blast furnace gas is required2≤30mg/m³、NOxCarrying out fruit thinning according to 50mg/m or less, carrying out fruit thinning according to 5mg/m or less. Therefore, the comprehensive utilization and purification of blast furnace gas must be performed simultaneously.
Compared with the traditional wet dust removal method, the blast furnace gas adopts dry dust removal, can recover and utilize sensible heat of the gas, save water and electricity, reduce the occupied area of industry, and improve TRT (blast furnace top gas recovery turbine) generating capacity and dust removal rate, so that the blast furnace gas is favored by various iron and steel enterprises. The wet dust removal method can simultaneously remove harmful substances such as sulfur, chlorine and nitrogen in the gas, and the energy-saving and environment-friendly dry dust removal method needs to add purification equipment, so that the problem that the iron and steel enterprises need to solve urgently is solved by efficiently removing impurities such as cyanic acid, chlorine, sulfur and the like in the blast furnace gas and further slowing down or solving the problems of salt accumulation and corrosion of the equipment.
Patent CN106435077B discloses a dry purification method and system for blast furnace gas, the method comprises a chemical looping combustion reactor and two adsorption towers, carrier gas is heated by heat release of the chemical looping combustion reaction, high-temperature carrier gas is used for desorbing and regenerating adsorbent, and desorbed NH is3Introducing the gas into a chemical looping combustion reactor to perform reduction reaction with the oxidation state oxygen carrier, introducing air into the chemical looping combustion reactor to perform an oxidation regeneration process of the reduction state oxygen carrier after the desorption of the adsorbent in the adsorption tower is completed, and purifying the blast furnace gas by adopting the alternate adsorption and regeneration of two parallel adsorption towers. The process adopts a chemical adsorption method to adsorb acid gas, carbonyl sulfide, carbon disulfide and the like are not treated, and pollutants can still enter a gas combustion unit along with blast furnace gas, so that harmful substances in the discharged tail gas are still not solved.
Patent CN109609202A discloses a method for desulfurizing and purifying blast furnace gas, comprising the steps of: s1, the blast furnace gas enters an organic sulfur conversion device after being dedusted by a dry cloth bag dedusting device, and the organic sulfur is converted into H2S; s2, then, the mixed gas enters a residual pressure turbine power generation device to recover pressure energy and heat energy; and S3, the cooled blast furnace gas enters a wet desulphurization device to remove hydrogen sulfide, and then the blast furnace gas goes to each user device. The method can effectively remove sulfides in the coal gas, but oxygen in the blast furnace gas is not removed, and the oxygen can not only cause sulfation of the organic sulfur hydrolysis catalyst, but also easily react with desulfurization rich liquid in a wet desulfurization tower to separate out elemental sulfur, thereby causing pipeline blockage; in addition, the dechlorination of the invention needs to be separately provided with a dechlorination tower, thus increasing the cost input.
Disclosure of Invention
The invention aims to meet higher environmental protection requirements and demands, and develops a complete blast furnace gas purification process with high dechlorination and desulfurization efficiency and low construction or reconstruction cost aiming at the defects of the existing blast furnace gas purification process.
To realizeThe technical scheme of the invention is as follows: firstly, the pipeline between the gravity dust removal and the cloth bag dust removal is used as a deacidification fluidized bed reactor to remove hydrogen chloride and cyanic acid in blast furnace gas, and then the blast furnace gas enters a deoxidation reactor to catalyze and remove O2Then the organic sulfur is hydrolyzed into H in an organic sulfur hydrolysis conversion reactor2S, finally, entering a wet desulphurization system to remove sulfide, and specifically comprising the following steps:
a. the blast furnace gas firstly enters gravity dust removal, then enters cloth bag dust removal to filter dust in the gas, deacidification powder adsorbent is sprayed into a pipeline between the gravity dust removal and the cloth bag dust removal, hydrogen chloride and cyanic acid in the gas react with active components to be removed under certain conditions, deacidification saturated powder adsorbent is collected by the cloth bag dust removal, and the chlorine of the deacidified gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3；
b. B, the blast furnace gas treated in the step a enters a deoxidation reactor, and under certain reaction conditions and the action of a deoxidation catalyst, O in the gas2And H2Or CO is reacted to H2O or CO2Removing oxygen, oxygen-removing reactor, and removing O2The content is less than 80mg/m3；
c. The deoxidized blast furnace gas enters a residual pressure turbine power generation device to recover residual pressure and generate power by waste heat, then enters an organic sulfur hydrolysis conversion reactor, and carbonyl sulfide, carbon disulfide and water vapor in the blast furnace gas are subjected to hydrolysis reaction under certain conditions and under the action of an organic sulfur hydrolysis catalyst to be converted into H which is easy to remove2S, the hydrolysis conversion rate is more than 95 percent;
d. the blast furnace gas after hydrolysis conversion enters a wet desulphurization system for desulphurization, firstly, desulphurization absorption liquid is sprayed into a pipeline between an organic sulfur hydrolysis reactor and a desulphurization absorption tower, the blast furnace gas is cooled and coarsely desulfurized, then the cooled blast furnace gas is in countercurrent contact with the desulphurization absorption liquid in the desulphurization absorption tower for fine desulphurization, gas-liquid separation is carried out in the absorption tower, and the total sulfur content after purification is less than 10mg/Nm3The blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption rich solution reacts with air in a regeneration tank to be separated out and separate sulfur foam to obtain regeneration liquid, and the regeneration liquid is circularly absorbedAnd (6) recovering and desulfurizing.
The deacidification powder adsorbent in the step a comprises magnesium oxide as a main active ingredient, calcium oxide, manganese oxide and iron oxide as auxiliary agents, and the critical fluidization speed of the powder is 0.012 m.S-1。
The step a of spraying the deacidification powder adsorbent into the pipeline between the gravity dust removal and the cloth bag dust removal utilizes the pipeline as a deacidification fluidized bed reactor; the certain conditions are that the temperature is 110-250 ℃, and the blast furnace gas flow velocity is greater than the critical fluidization velocity of the powder adsorbent.
The chlorine and the cyanogen in the blast furnace gas treated by the step a are less than 0.1mg/m3(ii) a The decyanation and dechlorination can protect the deoxidation catalyst and the organic sulfur hydrolysis catalyst from poisoning.
The deoxygenation reactor in the step b and the organic sulfur hydrolysis conversion reactor in the step c both adopt radial flow reactors, so that the pressure drop of gas passing through the reactors is reduced, and the resistance of a single reactor is less than 3 kPa.
The deoxygenation reactor in the step b is filled with a deoxygenation catalyst, the catalyst takes at least one of a large-hole spherical A-type molecular sieve and cloverleaf-shaped mordenite as a carrier, takes Cu, Mn, Ti, Ce and Mo as active components and takes lanthanide metal as an auxiliary agent.
The certain reaction condition of the step b is that the space velocity is 3750-10000 h-1The temperature is 100-230 ℃.
And c, filling an organic sulfur hydrolysis conversion reactor with an organic sulfur hydrolysis catalyst, wherein the catalyst takes at least one of cloverleaf strip-shaped X-type molecular sieves or Y-type molecular sieves as a carrier, and takes multiple elements of Na, Mg, Ca, Fe, Co, Ti, Mo and W as active components.
The certain reaction condition in the step c is that the airspeed is 4000-10000 h-1The temperature is 50-120 ℃.
The wet desulphurization system in the step d adopts any one of a PDS method, a tannin extract method and an iron complexing method; the total sulfur content in the blast furnace gas after wet desulphurization is less than 10mg/Nm3。
The blast furnace gas purification process has the following beneficial effects: (1) the pipeline between the gravity dust removal and the cloth bag dust removal is fully utilized as a deacidification fluidized bed reactor, so that the investment cost is saved; the problem of corrosion of the whole purification system can be relieved by removing chlorine before cloth bag dust removal; (2) the deoxidation reactor and the organic sulfur hydrolysis conversion reactor both adopt radial flow reactors, so that the pressure drop of gas passing through the reactors can be effectively reduced, and the resistance of a single reactor is less than 3 kPa; (3) the pipeline between the organic sulfur hydrolysis reactor and the wet desulphurization system is fully utilized as the desulphurization absorption reactor, so that the design capacity of the desulphurization absorption tower can be reduced, the temperature of coal gas can be reduced as much as possible in the pipeline, and the cost investment of a cooling tower or heat exchange equipment is reduced; (4) the oxygen in the coal gas is removed, so that the phenomenon that the pipeline is blocked due to elemental sulfur separated out by the reaction of the desulfurization rich solution in the pipeline or the absorption tower and the oxygen can be avoided; (5) the desulfurization powder adsorbent, the deoxidation catalyst and the organic sulfur hydrolysis catalyst have wide application temperature range, and can be directly used without changing the temperature of blast furnace gas by heat exchange. In conclusion, the process can simultaneously remove sulfides, chlorides, cyanic acid and the like in the blast furnace gas, has the characteristics of high removal precision, simple flow, small pressure drop and temperature drop, simple equipment, less investment, low operation cost and small occupied area, and has obvious advantages of the whole technology and economy.
Drawings
FIG. 1 is a process flow diagram of the dechlorination, desulfurization and purification process of blast furnace gas.
In fig. 1, 1 is gravity dust removal, 2 is bag dust removal, 3 is a deoxidation reactor, 4 is a residual pressure turbine power generation device (TRT), 5 is an organic sulfur hydrolysis conversion reactor, 6 is a desulfurization absorption tower, 7 is a regeneration tank, and 8 is a sulfur foam collecting tank.
Detailed Description
The invention will be further illustrated with reference to fig. 1 and the examples, but the invention is not limited to the examples.
The technological process of dechlorination, desulfurization and purification of blast furnace gas disclosed by the invention is shown in figure 1 and comprises the following steps:
a. blast furnace gas firstly enters a gravity dust removal device 1 and then enters a cloth bag dust removal device 2 to passFiltering dust in the coal gas; a pipeline A between the gravity dust removal 1 and the cloth bag dust removal 2 is used as a deacidification fluidized bed reactor, and a deacidification powder adsorbent is sprayed into the pipeline A; the gas flow velocity of the blast furnace is 0.012 m.S higher than the critical fluidization velocity of the powder adsorbent at the temperature of 110-250 DEG C-1Under the condition, hydrogen chloride and cyanic acid in the coal gas react with active components to be removed, and a cloth bag dust removal 2 is utilized to collect deacidification saturated powder adsorbent; the deacidified chlorine in the gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3。
b. B, allowing the blast furnace gas treated in the step a to enter a radial flow deoxygenation reactor 3, wherein the pressure drop of a bed layer is less than 3 kPa; at the airspeed of 3750-10000 h-1At a temperature of 100 to 230 ℃ and O2And H2Or CO is reacted to H2O or CO2Removing oxygen; after passing through a deoxygenation reactor, O2The content is less than 80mg/m3。
c. The deoxidized blast furnace gas enters a residual pressure turbine power generation device 4 to recover residual pressure and generate power by waste heat, and then enters an organic sulfur hydrolysis conversion reactor 5 at the airspeed of 4000-10000 h-1Under the conditions of 50-120 ℃ and the catalytic action of the organic sulfur hydrolysis catalyst, carbonyl sulfide, carbon disulfide and water vapor in blast furnace gas are subjected to hydrolysis reaction and converted into H which is easy to remove2S。
d. The blast furnace gas after hydrolysis and conversion enters a wet desulphurization system; firstly, spraying desulfurization absorption liquid into a pipeline B between an organic sulfur hydrolysis reactor 5 and a desulfurization absorption tower 6 to carry out temperature reduction and primary desulfurization on blast furnace gas; the cooled blast furnace gas is in countercurrent contact with desulfurization absorption liquid in a desulfurization absorption tower 6 for fine desulfurization, and gas-liquid separation is carried out in the absorption tower; the purified blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption pregnant solution reacts with air in the regeneration tank 7 to be separated out and sulfur foam is separated to obtain a regeneration solution, and the regeneration solution circularly absorbs desulfurization.
Example 1
The dechlorinating, desulfurizing and purifying process of blast furnace gas in certain steel and iron works in Shanxi is shown in attached figure 1. The gas amount of the raw material gas is 400000Nm3The temperature is 130-250 ℃, and the components, harmful substances and the content of the harmful substances are shown in table 1.
TABLE 1 composition of feed gases and harmful substances and their contents
| Components | content/V% | Hazardous substances | content/mg/Nm3 |
| CO | 24 | HCN | 17 |
| H2 | 4.1 | HCl | 36.4 |
| CO2 | 13.8 | H2S | 15.3 |
| N2 | 57.5 | COS | 122.6 |
| O2 | 0.6 | CS2 | 19.8 |
| H2O | Saturated steam |
The specific purification steps are as follows:
a. the blast furnace gas firstly enters a gravity dust removal device 1 and then enters a cloth bag dust removal device 2 to filter dust in the gas; a pipeline A between the gravity dust removal 1 and the cloth bag dust removal 2 is used as a deacidification fluidized bed reactor, and a deacidification powder adsorbent is sprayed into the pipeline A; the deacidification powder adsorbent comprises magnesium oxide as a main active component and calcium oxide, manganese oxide and iron oxide as auxiliaries; the gas flow velocity of the blast furnace is 0.012 m.S higher than the critical fluidization velocity of the powder adsorbent at the temperature of 130-250 DEG C-1Under the condition, hydrogen chloride and cyanic acid in the coal gas react with active components to be removed, and a cloth bag dust removal 2 is utilized to collect deacidification saturated powder adsorbent; the deacidified chlorine in the gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3(ii) a And the temperature of the blast furnace gas after the dry dedusting 2 is 120-230 ℃.
b. B, allowing the blast furnace gas treated in the step a to enter a radial flow deoxidation reactor 3, wherein the pressure drop of a bed layer is less than 3kPa, the reactor is filled with 40m deoxidation catalyst which takes a macroporous spherical A-type molecular sieve and cloverleaf strip-shaped mordenite as carriers, Cu, Mn, Ti, Ce and Mo as active components and lanthanide metal as an auxiliary agent3(ii) a At airspeed of 10000h-1The temperature is 120-230 ℃ and the O in the coal gas is under the catalytic action of a deoxidation catalyst2And H2Or CO is reacted to H2O or CO2Removing oxygen; after passing through a deoxidation reactor, blast furnace gas O2The content is less than 80mg/m3(ii) a Deoxidation belongs to exothermic reaction, and the outlet temperature of the deoxidation reactor 3 is maintained at 120-230 ℃.
c. Blast furnace gas entry residue after deoxidationThe pressure turbine power generation device 4 recovers residual pressure and generates power by using the residual pressure, and the temperature of blast furnace gas at a TRT outlet is 50-120 ℃; then the organic sulfur hydrolysis conversion catalyst enters a radial flow organic sulfur hydrolysis conversion reactor 5, the pressure drop of a bed layer is less than 3kPa, the reactor is filled with 100m organic sulfur hydrolysis catalyst which takes cloverleaf strip-shaped X-type molecular sieves and Y-type molecular sieves as carriers and takes Na, Mg, Co, Ti, Mo and W elements as active components3(ii) a At the airspeed of 4000h-1Under the condition that the temperature is 50-120 ℃, the organic sulfur hydrolysis catalyst catalyzes carbonyl sulfide, carbon disulfide and water vapor in blast furnace gas to perform hydrolysis reaction, and the carbonyl sulfide, the carbon disulfide and the water vapor are converted into H which is easy to remove2S; the conversion rate of carbonyl sulfide and carbon disulfide into inorganic sulfur through catalytic hydrolysis is more than 95%.
d. The blast furnace gas after hydrolytic conversion enters a complex iron wet desulphurization system, firstly, a desulphurization absorption liquid is sprayed into a pipeline B between an organic sulfur hydrolysis reactor 5 and a desulphurization absorption tower 6, and the blast furnace gas is cooled and subjected to coarse desulphurization to ensure that the temperature of the blast furnace gas is lower than 80 ℃; the cooled blast furnace gas is in countercurrent contact with desulfurization absorption liquid in a desulfurization absorption tower 6 for fine desulfurization, and gas-liquid separation is carried out in the absorption tower; the purified blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption pregnant solution reacts with air in a regeneration tank 7 to be separated out and sulfur foam is separated to obtain a regeneration solution, and the regeneration solution circularly absorbs desulfurization; the total sulfur content in the blast furnace gas after wet desulphurization is less than 10mg/Nm3。
Example 2
After the blast furnace gas of a certain steel plant in Hebei exceeds the standard after being combusted, the purification process is reconstructed on the basis of the original wet desulphurization, TRT power generation equipment is added to increase the attached economic benefit, and the existing dechlorination desulphurization purification process is shown as the attached drawing 1. The gas amount of the raw material gas is 300000Nm3The temperature is 110-230 ℃, and the components, harmful substances and the content thereof are shown in Table 2.
TABLE 2 composition of feed gas and harmful substances and their contents
| Components | content/V% | Hazardous substances | content/mg/Nm3 |
| CO | 24.2 | HCN | 13.2 |
| H2 | 5.9 | HCl | 29.9 |
| CO2 | 16.8 | H2S | 11.4 |
| N2 | 52.8 | COS | 154.7 |
| O2 | 0.3 | CS2 | 38.3 |
| H2O | Saturated steam |
The specific purification steps are as follows:
a. the blast furnace gas firstly enters a gravity dust removal device 1 and then enters a cloth bag dust removal device 2 to filter dust in the gas; a pipeline A between the gravity dust removal 1 and the cloth bag dust removal 2 is used as a deacidification fluidized bed reactor, and a deacidification powder adsorbent which takes magnesium oxide as an active ingredient and calcium oxide, manganese oxide and iron oxide as auxiliaries is sprayed into the pipeline A; the gas flow velocity of the blast furnace coal gas is 0.012 m.S higher than the critical fluidization velocity of the powder adsorbent at the temperature of 110-230 DEG C-1Under the condition, hydrogen chloride and cyanic acid in the coal gas react with active components to be removed, and a cloth bag dust removal 2 is utilized to collect deacidification saturated powder adsorbent; the deacidified chlorine in the gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3(ii) a And the temperature of the blast furnace gas after the dry dedusting 2 is 100-215 ℃.
b. B, allowing the blast furnace gas treated in the step a to enter a radial flow deoxidation reactor 3, wherein the pressure drop of a bed layer is less than 3kPa, the reactor is filled with a deoxidation catalyst 80m which takes a macroporous spherical A-type molecular sieve and cloverleaf strip-shaped mordenite as carriers, Cu, Mn, Ti, Ce and Mo as active components and lanthanide metal as an auxiliary agent3(ii) a At the space velocity of 3750h-1At the temperature of 100-215 ℃, the deoxidation catalyst catalyzes O in the coal gas2And H2Or CO is reacted to H2O or CO2Removing oxygen; after passing through a deoxidation reactor, blast furnace gas O2The content is less than 50mg/m3(ii) a Deoxidation belongs to exothermic reaction, and the outlet temperature of the deoxidation reactor 3 is maintained at 100-215 ℃.
c. The deoxidized blast furnace gas enters a residual pressure turbine power generation device 4 to recover residual pressure and generate power by using residual heat, and the temperature of the blast furnace gas at the TRT outlet is 50-100 ℃; then the organic sulfur enters a radial flow organic sulfur hydrolysis conversion reactor 5, the pressure drop of a bed layer is less than 3kPa, and 30m of organic sulfur hydrolysis catalyst which takes clover strip-shaped X-type molecular sieve as a carrier and takes Na, Mg, Ca, Fe, Co and Ti as active components is filled in the reactor3(ii) a In the skyThe speed is 10000h-1Under the condition that the temperature is 50-100 ℃, the organic sulfur hydrolysis catalyst catalyzes carbonyl sulfide, carbon disulfide and water vapor in blast furnace gas to perform hydrolysis reaction, and the carbonyl sulfide, the carbon disulfide and the water vapor are converted into H which is easy to remove2S; the conversion rate of carbonyl sulfide and carbon disulfide into inorganic sulfur through catalytic hydrolysis is more than 97%.
d. The blast furnace gas after hydrolysis conversion enters a PDS wet desulphurization system; firstly, spraying desulfurization absorption liquid into a pipeline B between an organic sulfur hydrolysis reactor 5 and a desulfurization absorption tower 6, and carrying out temperature reduction and coarse desulfurization on blast furnace gas to enable the temperature to be lower than 70 ℃; the cooled blast furnace gas is in countercurrent contact with desulfurization absorption liquid in a desulfurization absorption tower 6 for fine desulfurization, and gas-liquid separation is carried out in the absorption tower; the purified blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption pregnant solution reacts with air in a regeneration tank 7 to be separated out and sulfur foam is separated to obtain a regeneration solution, and the regeneration solution circularly absorbs desulfurization; the total sulfur content in the blast furnace gas after wet desulphurization is less than 10mg/Nm3。
Claims (10)
1. A blast furnace gas dechlorination, desulfurization and purification process is characterized by comprising the following steps:
a. the blast furnace gas firstly enters gravity dust removal, then enters a cloth bag dust removal to filter dust in the gas, deacidification powder adsorbent is sprayed into a pipeline between the gravity dust removal and the cloth bag dust removal, hydrogen chloride and cyanic acid in the gas react with active components under a certain condition to be removed, and deacidification saturated powder adsorbent is collected by the cloth bag dust removal; the deacidified chlorine in the gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3；
b. B, the blast furnace gas treated in the step a enters a deoxidation reactor, and under certain reaction conditions and the action of a deoxidation catalyst, O in the gas2And H2Or CO is reacted to H2O or CO2Removing oxygen, oxygen-removing reactor, and removing O2The content is less than 80mg/m3；
c. The deoxidized blast furnace gas enters a residual pressure turbine power generation device to recover residual pressure and generate power by waste heat, then enters an organic sulfur hydrolysis conversion reactor, and is subjected to reaction under certain conditionsUnder the action of organic sulfur hydrolysis catalyst, carbonyl sulfide, carbon disulfide and water vapor in blast furnace gas are subjected to hydrolysis reaction and converted into H easy to remove2S, the hydrolysis conversion rate is more than 95 percent;
d. the blast furnace gas after hydrolysis conversion enters a wet desulphurization system for desulphurization, firstly, desulphurization absorption liquid is sprayed into a pipeline between an organic sulfur hydrolysis reactor and a desulphurization absorption tower, the blast furnace gas is cooled and coarsely desulfurized, then the cooled blast furnace gas is in countercurrent contact with the desulphurization absorption liquid in the desulphurization absorption tower for fine desulphurization, gas-liquid separation is carried out in the absorption tower, and the total sulfur content after purification is less than 10mg/Nm3The blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption rich solution reacts with air in a regeneration tank to be separated out and sulfur foam is separated to obtain a regeneration solution, and the regeneration solution circularly absorbs desulfurization.
2. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the deacidification powder adsorbent in the step a comprises magnesium oxide as a main active ingredient, calcium oxide, manganese oxide and iron oxide as auxiliary agents, and the critical fluidization speed of the powder is 0.012 m.S-1。
3. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the step a of spraying the deacidification powder adsorbent into the pipeline between the gravity dust removal and the cloth bag dust removal utilizes the pipeline as a deacidification fluidized bed reactor; the certain conditions are that the temperature is 110-250 ℃, and the blast furnace gas flow velocity is greater than the critical fluidization velocity of the powder adsorbent.
4. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the chlorine and the cyanogen in the blast furnace gas treated by the step a are less than 0.1mg/m3(ii) a The decyanation and dechlorination can protect the deoxidation catalyst and the organic sulfur hydrolysis catalyst from poisoning.
5. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the deoxygenation reactor in the step b and the organic sulfur hydrolysis conversion reactor in the step c both adopt radial flow reactors, so that the pressure drop of gas passing through the reactors is reduced, and the resistance of a single reactor is less than 3 kPa.
6. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the deoxygenation reactor in the step b is filled with a deoxygenation catalyst, the catalyst takes at least one of a large-hole spherical A-type molecular sieve and cloverleaf-shaped mordenite as a carrier, takes Cu, Mn, Ti, Ce and Mo as active components and takes lanthanide metal as an auxiliary agent.
7. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the certain reaction condition of the step b is that the space velocity is 3750-10000 h-1The temperature is 100-230 ℃.
8. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: and c, filling an organic sulfur hydrolysis conversion reactor with an organic sulfur hydrolysis catalyst, wherein the catalyst takes at least one of cloverleaf strip-shaped X-type molecular sieves or Y-type molecular sieves as a carrier, and takes multiple elements of Na, Mg, Ca, Fe, Co, Ti, Mo and W as active components.
9. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the certain reaction condition in the step c is that the airspeed is 4000-10000 h-1The temperature is 50-120 ℃.
10. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the wet desulphurization system in the step d adopts any one of a PDS method, a tannin extract method and an iron complexing method; the total sulfur content in the blast furnace gas after wet desulphurization is less than 10mg/Nm3。
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