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WO2008052465A1 - Procédé de désulfuration et de dépoussiérage par voie humide de gaz de carneau calciné - Google Patents

Procédé de désulfuration et de dépoussiérage par voie humide de gaz de carneau calciné Download PDF

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Publication number
WO2008052465A1
WO2008052465A1 PCT/CN2007/070951 CN2007070951W WO2008052465A1 WO 2008052465 A1 WO2008052465 A1 WO 2008052465A1 CN 2007070951 W CN2007070951 W CN 2007070951W WO 2008052465 A1 WO2008052465 A1 WO 2008052465A1
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WIPO (PCT)
Prior art keywords
flue gas
desulfurization
sintering
wet
slurry
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.)
Ceased
Application number
PCT/CN2007/070951
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English (en)
French (fr)
Inventor
Xiaolin Shen
Hongzhi Shi
Guomin Shi
Daoqing Liu
Yu Lin
Lei Shi
Ruyi Wang
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Baoshan Iron and Steel Co Ltd
Original Assignee
Baoshan Iron and Steel Co Ltd
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Application filed by Baoshan Iron and Steel Co Ltd filed Critical Baoshan Iron and Steel Co Ltd
Priority to KR1020097010370A priority Critical patent/KR101140748B1/ko
Priority to BRPI0718179-5A priority patent/BRPI0718179B1/pt
Publication of WO2008052465A1 publication Critical patent/WO2008052465A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/16—Sintering; Agglomerating
    • C22B1/20—Sintering; Agglomerating in sintering machines with movable grates
    • 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
    • B01D53/50—Sulfur 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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • 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
    • 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
    • B01D53/70—Organic halogen 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
    • B01D53/74—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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/16—Sintering; Agglomerating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2047—Hydrofluoric acid
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a sintering flue gas desulfurization and dust removal process, in particular to a wet desulfurization and dust removal process for steel metallurgy sintering flue gas. Background technique
  • the sintering flue gas has become a major iron and steel smelting so 2 emission sources, and domestic research on sintering flue gas desulphurization technology basically blank, which has become a bottleneck restricting the development of China's iron and steel industry.
  • the existing countermeasures are mainly two.
  • low-sulfur fuel is used or a desulfurizing agent is added to the sintering raw material to reduce the emission of so 2.
  • a desulfurizing agent is added to the sintering raw material to reduce the emission of so 2.
  • Chinese patent CN1285415A performs desulfurization in combustion by adding an ammonia-containing compound to the sintering raw material. Due to the uneven distribution of the additive layer and the uneven temperature and concentration field in the combustion zone, the desulfurization efficiency of the method is not high.
  • the second is to desulfurize the sintering flue gas.
  • the flue gas desulfurization technology includes dry and wet methods.
  • the dry process includes a circulating fluidized bed method, a rotary spray method, an activated carbon adsorption method, an electron beam irradiation method, and the like.
  • the desulfurization efficiency corresponding to the circulating fluidized bed method and the rotary spray method is not high, generally 70 ⁇ 85 %; and the by-product after purification is unstable and difficult to use calcium sulfite, such as long-term stacking will cause a large site. Occupied, and will cause secondary pollution.
  • the activated carbon adsorption method has application performance in Japanese steel companies. For example, the No.
  • Japan's Kitakyushu Steel Works sprayed magnesium hydroxide solution into the sintering flue gas to convert S0 2 to magnesium sulfate, which was then separated from the sintering process by a scrubber.
  • Japanese Keihin sintered iron flue gas desulfurization using the ammonia-ammonium sulfate method this method is useless coke oven gas and ammonia sintering reaction S0 2 in the flue gas recovered ammonium sulfate.
  • the S0 2 solution is absorbed by ammonium sulfite solution (concentration: 3%) to form ammonium hydrogen sulfite, and the absorption liquid is sent to the coking plant to absorb NH 3 in the coke oven gas to form ammonium sulfite, which is then sent back to the sintering.
  • Ammonium sulfite solution concentration: 3%) to form ammonium hydrogen sulfite
  • the absorption liquid is sent to the coking plant to absorb NH 3 in the coke oven gas to form ammonium sulfite, which is then sent back to the sintering.
  • Limestone-gypsum method is used in the sinter plants in Chiba, Mizushima, Kashima, and Kobe in Japan. This type of process equipment was built in the 1970s. It adopts the most traditional limestone-gypsum process in the early stage. The level of process equipment is relatively backward, and the cost and operation cost are relatively high. Experts in the industry have always believed that
  • the absorption towers are in different forms, and the desulfurization efficiency, system cost, operating cost, and system operation stability are also different.
  • the limestone-gypsum absorption tower which is relatively mature and widely used in the world, is a spray tower. This type of tower has been widely used in thermal power units of 300,000 kilowatts or more at home and abroad.
  • the sintering flue gas has the following characteristics:
  • the concentration of S0 2 in the sintering flue gas is relatively low (generally 300 ⁇ 1000mg/Nm 3 ), and the lower limit is even lower than that of the flue gas after the wet desulfurization of the coal-fired boiler;
  • the concentration of S0 2 fluctuates greatly.
  • the gas-liquid mass transfer efficiency of the spray tower is generally high. To remove such a low concentration of S0 2 , it is necessary to ensure that the spray slurry is sufficiently covered in the cross section of the absorption tower, and even the coverage between the spray layer and the layer exceeds 200%. Therefore, the corresponding liquid-gas ratio (W/G) is large (generally W/G is 12 to 20), the power consumption is large, and the economy is poor.
  • the temperature of the sintering flue gas from the electrostatic precipitator is relatively low (85 ⁇ 150 °C), which makes the regenerative gas heat exchanger (GGH) at the front of the spray tower unable to remove the purified flue gas. Heat again to above 80 °C.
  • the composition of the sintering flue gas is complicated, which will worsen the working condition of the GGH which is more likely to be blocked, thereby reducing the availability of the system.
  • the composition of the sintering flue gas is complex. Depending on the sinter ore, the sulphur gas per cubic meter contains tens or even hundreds of milligrams of HF gas. In addition, the content of HC1 gas and heavy metals in the sintering flue gas is high, and the dust adsorption and adsorption are strong. These characteristics of the sintering flue gas put forward higher requirements for anti-corrosion and anti-scaling performance of the absorption tower and the whole desulfurization system, and wastewater treatment.
  • the technical problem to be solved by the invention is to provide a wet flue gas desulfurization and dedusting process for sintering flue gas, which has high efficiency of sintering flue gas desulfurization and dust removal, low energy consumption, low operation cost, small volume, low cost, reliable operation, etc.
  • the process is suitable for different sintering flue gas volumes, and can adapt to a wide range of sintering flue gas temperature and smoke composition changes.
  • the sintering flue gas from the precipitator is boosted by the booster fan, it is first cooled and defluorinated, that is, the HF, HC1 gas and large particle soot in the flue gas are basically removed by the alkali solution, and the temperature of the flue is lowered. Up to 80 °C;
  • the purified flue gas enters the mist eliminator to remove droplets from the flue gas, and is then reheated and discharged from the chimney.
  • HF gas is extremely corrosive, and the hydrofluoric acid formed after being dissolved in water will cause serious corrosion to the internal components of the absorption tower and the anticorrosive material, and is particularly destructive to the FRP material, thereby reducing the reliability of the operation of the desulfurization system.
  • the flue gas is cooled and defluorinated before entering the absorption tower.
  • the flue gas reacts with the fresh alkali solution from the lye tank to substantially remove the HF gas therein; at the same time, the evaporation of the lye and the process water reduce the temperature of the flue gas to below 80 ° C for subsequent desulfurization.
  • the intake air temperature of the absorption tower is lowered to below 80 ° C, which is beneficial to the long-term use of the absorption tower material, and ensures the thermal safety of the absorption tower. Since the HC1 gas in the flue gas also has an extremely high solubility, most of the HC1 is removed during cooling defluorination, and large particles of soot are removed.
  • the flue gas after cooling and defluorination enters the high-efficiency desulfurization absorption tower unique to the process, and the S0 2 therein is substantially removed by reacting with the alkali liquid in the absorption tower. Since the concentration of S0 2 in the sintering flue gas is low, as in the case of the conventional spray tower, high power consumption is required to achieve higher desulfurization efficiency. Therefore, this process uses a specially designed desulfurization absorber.
  • the absorption tower does not adopt the traditional slurry circulation cycle and the upper spray method, but allows the flue gas after cooling fluorine to be uniformly transferred from the middle of the absorption tower into a plurality of vent pipes arranged in a certain manner in the tower, the vent tube
  • the lower vent is immersed under the surface of the absorbent slurry.
  • the flue gas passes through the swirling device in the jet tube, it generates a strong rotation, and then rushes from the vent hole into the absorption tower slurry tank.
  • the bubbles are mutually opposed, rotated, sheared and broken after being flushed out, in the slurry. Be further Breaking, enhanced gas-liquid contact effect, in this process can achieve more than 95% desulfurization efficiency and more than 99% of dust removal efficiency.
  • the lower part of the absorption tower slurry tank is a stirring mechanism and an oxidizing device.
  • the purpose of the agitation mechanism is to prevent precipitation of gypsum at the bottom of the slurry tank; the function of the oxidation mechanism is to further oxidize the by-products of the reaction into usable gypsum crystals.
  • concentration of the gypsum slurry at the bottom of the absorption tower slurry tank reaches a set value, the gypsum slurry is discharged from the bottom of the tower and enters a subsequent gypsum dewatering system.
  • the purified flue gas enters the demister, and the flue gas after defogging achieves a good droplet separation effect.
  • the flue gas after the de-fog is reheated and discharged from the chimney.
  • the gypsum slurry produced after desulfurization is subjected to two-stage dehydration, and the water content is reduced to less than 10%, and the two-stage dehydration is respectively performed by a screw discharge sedimentation centrifuge or a hydrocyclone separator and a vacuum belt conveyor. . .
  • the sintering flue gas is cooled and defluorinated, and is carried out in a cooling defluorinator. This will better ensure that the temperature of the smoke is rapidly reduced to below 80 ° C, while substantially removing the HF gas from the flue gas.
  • the temperature of the flue gas in step 1) is cooled by the evaporation of the lye and the process water in the cooled defluorinator.
  • the waste water generated in the cooling defluorinator is directly discharged into the wastewater treatment system.
  • the waste water generated in the cooling defluoridation unit contains F_, Cl_, heavy metal-containing soot and a small amount of calcium sulphite, and the amount of waste water is not large, so it is directly discharged into the wastewater treatment system, and no longer enters the subsequent desulfurization tower.
  • the chloride ion and heavy metal enrichment effects of the desulfurization system are greatly alleviated, the chlorine corrosion problem of the subsequent equipment is alleviated, and the grade of desulfurization by-product gypsum is improved.
  • the waste water discharged from the cooling defluoridation device separates the heavy metal in the waste water by a process such as sedimentation and pH adjustment, and the dried heavy metal sludge is recovered by magnetic separation to recover the iron therein.
  • the iron then returns to the sintering head to participate in the ore blending.
  • the flue gas after cooling and defluorination is passed through the action of the swirling device in the gas injection tube in the absorption tower, and is rapidly swirled into the slurry pool, and the flue gas is The slurry is broken and thoroughly mixed with it, and the gas and liquid complete the desulfurization and dust removal process during the high-efficiency contact process.
  • the high-efficiency desulfurization absorber in step 2) has no slurry circulation pump, so the operating cost is low.
  • the gas flow rate in the absorption tower is high, so the tower body structure is relatively compact and the floor space is small.
  • the reheating process of the flue gas after the demisting by the step 3) is carried out by using the sintering waste heat vapor of the system.
  • the waste heat vapor generated during the cooling and sinter of the ring cooler is introduced into the steam flue gas reheater, so that the flue gas temperature is heated to 80 ° C and then discharged from the chimney.
  • This method of using the residual heat of steam to replace the conventional regenerative gas heat exchanger (GGH) eliminates the expensive GGH and avoids the occurrence of clogging, thereby improving the stability of the system operation and reducing the investment. cost.
  • alkali solution can be used as long as the basic substance the reaction of S0 2 is configured to solution or slurry.
  • desulfurized alkaline materials are calcium-based absorbents such as limestone and slaked lime, which have a good price advantage.
  • Other basic compounds such as sodium, magnesium and ammonium may also be used.
  • the gypsum in this patent refers to any sulfate formed after the above-mentioned alkaline substance is desulfurized.
  • 1 can adapt the amount of sintering gas, flue gas temperature and flue gas so 2 concentration in a wide range of requirements, more than 95% desulfurization efficiency, collection efficiency of 99%, in particular for submicron dust good Remove the effect.
  • the measure ensures the thermal safety of the absorption tower, effectively reduces the corrosion problem in the tower, and improves the reliability of the operation of the desulfurization system.
  • the absorption tower inside the process has no moving parts and no nozzle inside, which reduces the possibility of scale formation, high reliability of equipment operation and greatly reduced maintenance.
  • the absorption tower used in this process has no slurry circulation pump, so the operation cost is low. Moreover, the gas flow rate in the absorption tower is high, so the tower body structure is relatively compact and the floor space is small.
  • Figure 1 is a schematic view of the process flow of the present invention.
  • the sintering flue gas to be treated from the electrostatic precipitator 6 is first pressurized by the turbocharger 7, and then enters the cooling defluoridation unit 8 located at the front of the desulfurization absorption tower 9 for defluorination cooling.
  • the flue gas is reacted with the fresh alkali solution sprayed from the limestone slurry tank 14 into the cooling defluoridation unit 8 and washed by the process water sprayed from the process water tank 13, so that the HF gas in the sintering flue gas can be substantially removed.
  • the temperature of the flue gas is reduced to below 80 ° C, which provides the best reaction conditions for subsequent desulfurization and ensures the thermal safety of the absorption tower. Since the HC1 gas in the flue gas also has an extremely high solubility, most of the HC1 is removed while cooling the defluorination, while removing large particles of soot.
  • the wastewater generated by the cooling defluoridation unit 8 is directly discharged into the wastewater treatment system 15 .
  • the waste water generated in the cooling defluoridation unit 8 contains F_, Cl_, heavy metal-containing soot and a small amount of calcium sulfite, and the amount of waste water is not large, so it is directly discharged into the wastewater treatment system, and no longer enters the subsequent desulfurization tower.
  • the chloride ion and heavy metal enrichment effects of the desulfurization system are greatly reduced, the chlorine corrosion problem of the subsequent equipment is alleviated, and the grade of desulfurization by-product gypsum is improved.
  • the waste water discharged from the cooling defluoridation unit 8 is separated from the heavy metal in the wastewater by a process such as sedimentation and pH adjustment in the wastewater treatment system 15, and the dried heavy metal sludge is magnetically selected by the magnetic separator 16 to recover the iron therein.
  • the recovered iron is returned to the head of the sintering machine 4 to participate in the ore blending. Thereby increasing the resource utilization of the sintering system.
  • the remaining heavy metals may be further utilized or sent out as appropriate.
  • the flue gas cooled from the cooling defluoridation device 8 uniformly enters a plurality of vent pipes arranged in a certain regular pattern in the desulfurization absorption tower 9, and the flue gas rotates downwardly in the tube by the action of the swirling device in the lance tube. It is sprayed into the lye along the tangential direction of the vent hole in the lower part of the lance. Due to the special arrangement of the vent tube, the jetted bubbles produce severe effects such as hedging, shearing, swirling, and crushing in the slurry. Thereby, a gas-liquid two-phase turbulent zone with high mixing and strong interference is generated, which greatly improves the gas-liquid mass transfer effect.
  • So 2 in the flue gas is dissolved in the liquid phase in the process of chemical absorption reaction, after removing the dust remaining in the flue gas are in contact with the liquid.
  • the bubbles in the turbulent zone continue to flicker up until they rupture on the top of the slurry, completing the entire flue gas scrubbing process.
  • the calcium sulfite formed after the reaction is further oxidized into calcium sulfate in the absorption tower slurry storage tank by the air blasted by the oxidation fan 12, and crystallized to form gypsum.
  • the agitator 5 at the bottom of the column is always running to prevent the gypsum slurry from settling.
  • the desulfurization absorption tower of the present invention may also adopt integral FRP (when the amount of flue gas is small) or carbon steel lining FRP (when the amount of flue gas is large) ) to manufacture.
  • FRP material has superior anti-corrosion and anti-fouling performance, and low cost; the defluorination cooling section 8 provides a reliable guarantee for the thermal safety and anti-corrosion safety of the FRP absorption tower.
  • the flue gas after desulfurization exits the desulfurization absorption tower 9 and enters the mist eliminator 10 for gas-liquid separation.
  • the flue gas from the mist eliminator 10 needs to be heated to 80 ° C in the steam flue gas reheater 3 before being discharged into the chimney 1 by the induced draft fan 2 .
  • the steam flue gas reheater uses a ring cooler to cool the waste heat vapor generated during the sintering process as a reheat heat source.
  • the gypsum slurry generated by the reaction of the flue gas in the desulfurization absorption tower 9 and the alkali solution enters the gypsum dehydration system 1 1 and is dehydrated by two stages.
  • the two-stage dewatering is performed by a screw discharge sedimentation centrifuge or a hydrocyclone separator and a vacuum belt conveyor, respectively. Since the concentration of S0 2 in the sintering flue gas is low, the gypsum output is not high.
  • a method of intermittent ointment is adopted. That is, the density of the gypsum slurry is regularly monitored by a densitometer.
  • the gypsum slurry is taken out from the bottom of the absorption tower by a gypsum removal pump, pumped to the gypsum slurry tank, and then sent to the screw discharge by the gypsum dewatering pump.
  • the centrifuge or hydrocyclone performs the first-stage dewatering, and the gypsum thickened by the first-stage dewatering is further dehydrated to a moisture content of about 10% by a vacuum belt conveyor.
  • the wet flue gas desulfurization and dust removal process of the sintering flue gas is controlled by a DCS distributed control system.
  • Test apparatus for a sintering hot flue gas desulfurization test from a sintering plant flue gas discharge flue gas temperature of 150 ° C, flow rate of 90000m 3 / h, converted into dry standard 57800 (N. d. m 3 ) /h.
  • the concentration of S0 2 in the flue gas is 300 ⁇ 800 mg/Nm 3
  • the concentration of HF is 50 ⁇ 90 mg/Nm 3
  • the concentration of HC1 is 80 ⁇ 150 mg/Nm 3
  • the dust concentration is 50 ⁇ 120 mg/Nm 3 .
  • the gas enters the absorption tower for reaction, the diameter of the tower is 4 m, the height of the slurry surface is 3.5 m, and the number of the jet tubes is 28, and the swirling device is located in the middle of the jet tube.
  • the absorbent is 15%wt limestone slurry, the amount of slurry is 250 ⁇ 500kg/h, stone
  • the limestone consumption is 37.6 ⁇ 75.2kg/ho.
  • the amount of 20%wt gypsum discharged is 0.3 ⁇ 0.6 m 3 /h.
  • the amount of oxidizing air was 3 m 3 /min, and the oxidizing air head was 49 kPa.
  • the flue gas temperature after desulfurization is 50 ° C, and the water droplet carrying capacity in the flue gas after two-stage demisting is less than 75 mg/Nm 3 ; the flue gas temperature rises to 80-90 ° C after reheating.
  • the desulfurization efficiency of the above desulfurization system is over 95%, the defluorination and dechlorination efficiency is over 95%, and the dust removal efficiency is 99%.
  • the amount of discharged gypsum slurry is 0.3 ⁇ 0.6 m 3 /h, and the water content after dewatering by the horizontal screw discharge sedimentation centrifuge is 50% ⁇ 60%, and the moisture content of the gypsum after dehydration by the vacuum belt machine is less than 10%.
  • the resulting gypsum crystal particles have a particle size of 46 to 100 ⁇ m.

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Description

烧结烟气湿法脱硫除尘工艺 技术领域
本发明涉及一种烧结烟气脱硫除尘工艺， 特别涉及一种用于钢铁冶金烧结 烟气的湿法脱硫除尘工艺。 背景技术
目前， 烧结烟气已成为钢铁冶炼中 so2的主要排放源， 而国内对烧结烟气 脱硫技术的研究基本属于空白， 这已成为制约我国钢铁行业发展的瓶颈。
为解决烧结烟气 so2的排放问题， 现有对策主要有两种。
一是选用低硫燃料或在烧结原料中添加脱硫剂以降低 so2的排放， 如中国 专利 CN1285415A 通过在烧结原料中添加含氨化合物来进行燃烧中脱硫。 由于 添加剂在料层分布不均及燃烧区温度、 浓度场的不均匀， 该法脱硫效率不高。
二是对烧结烟气进行脱硫， 烟气脱硫技术包括干法和湿法。 干法技术有循 环流化床法、 旋转喷雾法、 活性炭吸附法、 电子束辐照法等。 循环流化床法和 旋转喷雾法对应的脱硫效率不高， 一般在 70〜85 %； 而且净化后的副产物为不 稳定的、 难以利用的亚硫酸钙， 如长期堆放将造成很大的场地占用， 且会引起 二次污染。 活性炭吸附法在日本的钢铁企业有应用业绩， 如名古屋钢铁厂的 3 号烧结机设置了一套利用活性炭吸附的烧结烟气脱硫、 脱硝装置。 该方法虽能 达到 95 %的脱硫率和 40 %的脱硝率， 但活性炭价格昂贵， 净化系统和吸收剂 再生系统复杂， 因此投资和运行费用极高。 日本专利 JP52051846 公开了一种 电子束辐照法的工艺， 该工艺能达到 80 %以上的脱硫和脱硝率， 但耗能很高， 且有辐射泄漏的危险。 以上几种烧结烟气干法脱硫工艺， 对烟气中的细微粉尘 的脱除效果都不明显， 而且不具备对烧结烟气中的金属进行回收的相应措施。
与干法相比， 烧结烟气湿法脱硫工艺的应用更加广泛。 日本北九州制铁所 将氢氧化镁溶液喷洒于烧结烟气中， 使 S02转变为硫酸镁， 然后再经洗涤 塔将其从烧结生产过程中分离出来。 日本京滨制铁所采用氨一硫铵法进行烧结 烟气脱硫， 该方法是利用焦炉气中无用的氨与烧结烟气中的 S02反应回收硫铵。 首先用亚硫酸铵溶液（浓度为 3 % )吸收 S02并生成亚硫酸氢铵， 再将吸收液送 到焦化厂吸收焦炉煤气中的 NH3， 进而形成亚硫酸铵， 再被送回烧结厂以循环 往复利用。 日本的千叶、 水岛、 鹿岛、 神户等地的烧结厂皆采用石灰石一石膏 法。 该类工艺装置均为上世纪 70 年代建成， 采用早期最为传统的石灰石一石 膏工艺， 工艺装置水平比较落后， 造价和运行费用均较高。 行业内专家一直认 为国外的技术工艺复杂、 经济性较差， 在国内运行不可取。
湿法脱硫的关键设备 吸收塔的形式不同， 脱硫效率、 系统造价、 运行 费用以及系统运行稳定性等也不尽相同。 目前， 国际上比较成熟和应用最多的 石灰石一石膏法的吸收塔为喷淋塔， 该种塔型在国内外 30 万千瓦以上的火电 机组上已大量使用。 但与燃煤锅炉烟气不同， 烧结烟气存在以下特点：
( 1 ) 烧结烟气中 S02浓度较低 （一般在 300〜1000mg/Nm3 ) ， 其下限甚至 比燃煤锅炉烟气湿法脱硫后的排烟浓度更低； 而且烧结烟气量及其中的 S02浓 度波动较大，这些特点决定了烧结烟气脱硫须采用高效率、低投资的脱硫技术。 而喷淋塔气液传质效率一般， 若要脱除如此低浓度的 S02， 须确保喷淋浆液在 吸收塔截面上充分覆盖， 甚至喷淋层与层之间的覆盖率超过 200%， 由此对应的 液气比（W/G)较大 （一般 W/G在 12〜20 ) ， 动力消耗很大， 经济性较差。
( 2 ) 与燃煤锅炉烟气相比， 烧结烟气中粉尘微粒的粒径较小， 亚微米级 粉尘的份额较高， 传统的喷淋塔对此粒径范围的粉尘脱除效率不高。
( 3 ) 从电除尘器出来的烧结烟气温度相对较低 （85〜150°C ) ， 这使得喷 淋塔前部的蓄热式气气换热器 （GGH ) 无法将净化后的烟气再热到 80°C以上。 而且烧结烟气成分复杂， 这将使原本就较易堵塞的 GGH的工作状况更趋恶化， 从而降低了系统的可用性。
( 4 ) 烧结烟气成分复杂， 依据烧结矿的不同， 每立方米烧结烟气中含有 几十甚至几百毫克的 HF气体。 此外， 烧结烟气中 HC1气体和重金属的含量均 较高， 粉尘粘结吸附性强。 烧结烟气的这些特点对吸收塔及整套脱硫系统的防 腐防垢性能、 废水处理等提出了更高的要求。
因此， 考虑到烧结烟气的特殊性， 将在电厂脱硫中广泛应用的湿法脱硫工 艺和喷淋塔完全照搬到烧结烟气脱硫上来， 未必可行且不经济。 发明内容
本发明要解决的技术问题是提供一种烧结烟气湿法脱硫除尘工艺， 具有烧 结烟气脱硫除尘效率高、 能耗低、 运行费用省、 体积小、 造价低、 运行可靠等 特点， 以缓解烧结烟气中 so2的排放对生态环境和人体健康产生的影响， 并减 轻企业的经济损失和环境压力。 该工艺适用于不同烧结烟气量， 且能适应较大 范围的烧结烟温和烟气成分的变化。
本发明解决上述技术问题的技术方案的步骤包括：
1 ) 从除尘器出来的烧结烟气经增压风机升压后， 首先进行冷却脱氟， 即 利用碱液将烟气中的 HF、 HC1气体和大颗粒烟尘基本脱除， 同时将烟温降到 80 °C以下；
2 ) 烟气进入脱硫吸收塔， 烟气中的 S02与吸收塔内的碱液反应；
3 ) 净化后的烟气进入除雾器除去烟气中的液滴， 然后被再热后从烟囱排 出。
不同于燃煤锅炉烟气， 依据烧结矿的不同， 每立方米烧结烟气中含有几十 甚至几百毫克的 HF气体。 HF气体腐蚀性极强， 溶于水后生成的氢氟酸会对吸 收塔内构件及防腐材料产生严重的腐蚀， 对玻璃钢材料的破坏性尤其大， 从而 降低了脱硫系统运行的可靠性。 为保证吸收塔的安全运行、 降低塔内防腐材料 的等级并为后续的脱硫提供最佳的反应条件， 在烟气进入吸收塔前先对其进行 冷却脱氟。 在此过程中， 烟气与来自碱液槽的新鲜碱液反应， 可基本脱除其中 的 HF气体； 同时碱液的蒸发和工艺水使烟气温度降到 80 °C以下， 为后续的脱 硫提供最佳的反应条件。吸收塔如长期在 8CTC以上工作，无论是什么防腐材料， 都会出现材料疲劳老化、 使用寿命降低的问题。 因此将吸收塔的进气温度降到 80°C以下， 有利于吸收塔材料的长期使用， 保证了吸收塔的热安全性。 由于烟 气中的 HC1气体亦具有极高的溶解度， 因此在冷却脱氟时大部分的 HC1得以除 去， 同时除去大颗粒的烟尘。
经过冷却脱氟后的烟气进入该工艺特有的高效脱硫吸收塔， 通过与吸收塔 内的碱液反应， 基本除去其中的 S02。 由于烧结烟气中的 S02浓度较低， 如采用 传统的喷淋塔形式， 则要达到较高的脱硫效率需提供很高的动力消耗。 因此， 本工艺采用特殊设计的脱硫吸收塔。 该吸收塔不采用传统的浆液打循环、 上部 喷淋的方式， 而是让冷却氟脱后的烟气从吸收塔中部均匀地进入塔内按一定方 式排布的若干根喷气管中， 喷气管下部的排气孔浸没在吸收剂浆液面下。 烟气 经喷气管内的旋流装置后， 产生强烈旋转， 随后从排气孔沿切向冲入吸收塔浆 液池中， 气泡在冲出后发生相互对冲、 旋转、 剪切、 破碎， 在浆液中被进一步 打碎， 增强了气液接触效果， 在这一过程中能达到 95 %以上的脱硫效率和 99 %以上的除尘效率。 吸收塔浆液池下部为搅拌机构和氧化装置。 搅拌机构目的 是防止浆液池底部的石膏发生沉淀； 氧化机构的作用是将反应副产物进一步氧 化成可利用的石膏晶体。 当吸收塔浆液池底部的石膏浆液浓度达到设定值时， 石膏浆液由塔底排出并进入后续的石膏脱水系统。
净化后的烟气进入除雾器， 经除雾后的烟气达到良好的液滴分离效果。 除 雾后的烟气被再热后从烟囱排出。
作为本发明的一种改进， 其中脱硫后产生的石膏浆液经过两级脱水， 含水 率降到 10%以下， 两级脱水分别由螺旋卸料沉降离心机或水力旋流分离器和真 空皮带机完成。 。
作为本发明的一种改进， 对烧结烟气进行冷却脱氟， 在一冷却脱氟器中进 行。 这样能更好地保证将烟温迅速地降低到 80°C以下， 同时基本脱除烟气中的 HF气体。
作为本发明的另一种改进， 步骤 1 ) 中烟温是通过碱液的蒸发和冷却脱氟 器中的工艺水冷却的。
作为本发明的另一种改进， 冷却脱氟器中产生的废水直接排入废水处理系 统。 冷却脱氟器内产生的废水含有 F_、 Cl_、 含重金属的烟尘及少部分的亚硫 酸钙， 且废水量不大， 故直接排入废水处理系统， 而不再进入后续的脱硫塔。 从而大大减轻了脱硫系统的氯离子和重金属富集效应， 缓解了后续设备的氯腐 蚀问题， 并提高了脱硫副产石膏的品位。
作为本发明另外的改进， 从冷却脱氟器中排出的废水通过沉淀、 pH值调节 等工序将废水中的重金属分离出来， 烘干的重金属污泥经磁选后回收其中的 铁， 回收后的铁再返回烧结机头参与配矿。从而提高了烧结系统的资源利用率。
作为本发明的另一种改进， 在步骤 2 ) 的脱硫吸收塔中， 冷却脱氟后的烟 气通过吸收塔内喷气管中旋流装置的作用， 高速旋冲入浆液池中， 烟气在浆液 中被打碎并与之充分混合， 气液在高效接触过程中完成脱硫、 除尘过程。 步骤 2 ) 中的高效脱硫吸收塔无浆液循环泵， 因此运行费用低。 而且吸收塔内气流 速度高， 因此塔体结构较为紧凑， 占地面积小。 且脱硫吸收塔的内部无运动部 件、 无喷嘴， 从而大大降低了吸收塔的堵塞和结垢倾向， 系统运行可靠性高， 维修量减少。 作为本发明另外的改进， 经过步骤 3 ) 除雾后的烟气的再加热过程是通过 利用本系统的烧结余热蒸气来实现的。 即将环冷机冷却烧结矿过程中产生的余 热蒸气引入蒸气烟气再热器， 从而将烟气温度加热到 80 °C后再从烟囱排出。 这 种利用烧结余热蒸气的方式以代替传统的蓄热式气气换热器 (GGH)的工艺， 取 消了昂贵的 GGH又避免了堵塞的发生， 从而提高了系统运行的稳定性并降低了 投资成本。
至于上述的碱液， 只要是能与 S02反应的碱性物质配置成的溶液或浆液都 可使用。 常用的脱硫碱性物质为钙基吸收剂如石灰石和熟石灰， 因其具有较好 的价格优势。 其他如钠基、 镁基和铵基等碱性化合物亦可使用。
本专利中的石膏指上述碱性物质脱硫后形成的任意一种硫酸盐。
由于本发明采用了上述的技术方案， 使之与现有技术相比， 具有以下的优 点和积极效果：
1 . 能适应烧结烟气量、 烟气温度及烟气中 so2浓度变化范围较宽的要求， 脱硫效率达 95 %以上， 除尘效率达 99%， 尤其对亚微米级的粉尘有很好的脱除 效果。
2. 在吸收塔前单独设置一冷却脱氟器， 将烟温降到 80 °C以下的同时除去 大部分 HF 气体。 该措施在为后续的脱硫提供最佳反应条件的基础上， 保证了 吸收塔的热安全性， 有效地减轻了塔内的腐蚀问题， 提高了脱硫系统运行的可 靠性。
3. 在冷却脱氟器内同时除去大部分的 HC1 气体和大颗粒烟尘， 减轻了脱 硫系统的氯离子和重金属富集效应， 缓解了后续设备的氯腐蚀问题， 并提高了 脱硫副产石膏的品位。
4. 对冷却脱氟器产生的少量废水进行处理， 减小了废水处理量。 同时对 废水中的重金属尤其是铁进行回收并送至机头参与配矿， 提高了烧结系统的资 源利用率。
5. 与传统的喷淋塔相比， 本工艺采用的吸收塔内部无运动部件、 无喷嘴， 降低了结垢的可能性， 设备运行可靠性高， 维修量大大减小。
6. 与传统的喷淋塔相比， 本工艺采用的吸收塔无浆液循环泵， 因此运行 费用低。 而且吸收塔内气流速度高， 因此塔体结构较为紧凑， 占地面积小。
7. 本工艺采用的吸收塔， 烟气高速旋转冲入浆液池中， 气液接触效果好， 脱硫除尘效率高。
8. 针对烧结烟气的特点， 利用烧结余热蒸气再热的方式以代替传统的蓄 热式气气加热器， 取消了昂贵的 GGH又避免了堵塞的发生， 提高了系统运行的 稳定性并降低了投资成本。 附图概述
图 1为本发明的工艺流程示意图。
图 2为本发明的工艺系统简图。 本发明的最佳实施方案
由图 1至图 2可知， 从静电除尘器 6出来的待处理烧结烟气首先经增压风 机 7升压后， 进入位于脱硫吸收塔 9前部的冷却脱氟器 8进行脱氟冷却。 在此 阶段， 烟气与从石灰石浆液槽 14喷入冷却脱氟器 8 的新鲜碱液反应后， 并经 过工艺水槽 13喷入的工艺水洗涤， 可基本脱除烧结烟气中的 HF气体， 同时烟 气温度降低到 80°C以下， 为后续的脱硫提供最佳反应条件， 并保证了吸收塔的 热安全性。 由于烟气中的 HC1气体亦具有极高的溶解度， 因此在冷却脱氟的同 时大部分的 HC1得以除去， 同时除去大颗粒烟尘。
其中， 经冷却脱氟器 8中产生的废水直接排入废水处理系统 15。 冷却脱氟 器 8 内产生的废水含有 F_、 Cl_、 含重金属的烟尘及少部分的亚硫酸钙， 且废 水量不大， 故直接排入废水处理系统， 而不再进入后续的脱硫塔。 从而大大减 轻了脱硫系统的氯离子和重金属富集效应， 缓解了后续设备的氯腐蚀问题， 并 提高了脱硫副产石膏的品位。
从冷却脱氟器 8中排出的废水在废水处理系统 15通过沉淀、 pH值调节等 工序将废水中的重金属分离出来， 烘干的重金属污泥经磁选机 16 磁选后回收 其中的铁， 回收后的铁再返回烧结机 4的机头参与配矿。 从而提高了烧结系统 的资源利用率。 剩余的重金属可视情况进一步利用或外送处理。
从冷却脱氟器 8降温后的烟气均匀地进入脱硫吸收塔 9内按一定规律排布 的若干根喷气管中， 通过喷气管内的旋流装置的作用， 烟气在管内旋转向下运 动， 并沿喷气管下部的排气孔的切线方向喷入碱液中。 由于特殊的喷气管排布 方式， 使喷射出的气泡在浆液中产生剧烈的对冲、 剪切、 旋流、 破碎等效应， 从而产生一个高度掺混、 强烈干涉的气液两相紊流区， 极大地提升了气液传质 效果。 在这一过程中， 烟气中的 so2溶解在液相中进行化学吸收反应， 烟气中 的残留的粉尘也在接触液体后被除去。 紊流区内的气泡继续曲折上升， 直至在 浆液面上部破裂， 完成整个烟气洗涤过程。 反应后生成的亚硫酸钙通过氧化风 机 12 鼓入的空气， 进一步在吸收塔浆液贮罐中氧化成硫酸钙， 并结晶生成石 膏。 塔底部的搅拌器 5始终运行以防止石膏浆液沉淀。 本发明涉及的脱硫吸收 塔除常用的碳钢内衬玻璃鳞片或橡胶内衬材料外， 亦可采用整体玻璃钢 （处理 烟气量较小时） 或碳钢内衬玻璃钢 （处理烟气量较大时） 来制造。 玻璃钢材质 的防腐、 防结垢性能优越， 且造价低； 脱氟冷却段 8的设置更为玻璃钢吸收塔 的热安全性及防腐安全性提供了可靠的保障。
脱硫后的烟气从脱硫吸收塔 9 出来后进入除雾器 10进行气液分离。 从除 雾器 10出来的烟气需在蒸气烟气再热器 3中加热到 80°C后才能由引风机 2排 入烟囱 1。 蒸气烟气再热器利用环冷机冷却烧结矿过程中产生的余热蒸气来作 为再热热源。
烟气在脱硫吸收塔 9与碱液反应产生的石膏浆液进入石膏脱水系统 1 1 经 两级脱水。 两级脱水分别是由螺旋卸料沉降离心机或水力旋流分离器和真空皮 带机完成的。 由于烧结烟气中 S02浓度较低， 故石膏产量不高， 为减轻石膏处 理系统的负荷并便于脱水， 采取间歇出膏的方式。 即通过密度计定时监测石膏 浆液的密度， 当满足出膏要求时， 石膏浆液自吸收塔底部由石膏取出泵引出， 并泵送至石膏浆液槽， 然后再经石膏脱水泵送到螺旋卸料沉降离心机 （或水力 旋流分离器） 进行一级脱水， 经一级脱水稠化后的石膏进一步用真空皮带机脱 水到 10 %左右的含水率。
本烧结烟气湿法脱硫除尘工艺由 DCS集散型控制系统进行控制。
针对一烧结烟气脱硫的热态试验装置： 试验用烟气取自某烧结厂排放烟气， 温度为 150°C， 流量为 90000m3/h， 折合成标干态 5. 78万 (N. d. m3 ) /h。烟气中 S02 浓度为 300〜800 mg/Nm3， HF浓度为 50〜90 mg/Nm3， HC1浓度为 80〜150 mg/Nm3， 粉尘浓度为 50〜120 mg/Nm3。 烟温经冷却脱氟器后降至 80°C； 原烟气为 15CTC时， 冷却脱氟器内喷石灰石浆液量为 120〜250 kg/h， 冷却水量为 2 t/h0 冷却后的烟 气进入吸收塔进行反应， 塔直径 4m， 浆液面高度 3. 5m， 喷气管共 28根， 旋流装置 位于喷气管的中部。 吸收剂为 15%wt的石灰石浆液， 浆液量为 250〜500kg/h， 石 灰石耗量为 37.6〜75.2kg/ho 排出的 20%wt石膏量为 0.3〜0.6 m3/h。 氧化空气量 为 3m3/min， 氧化空气压头 49kPa。 脱硫后的烟气温度为 50°C， 经两级除雾后烟气 中水滴携带量小于 75 mg/Nm3; 再热后烟气温度上升到 80〜90°C。
上述脱硫系统的脱硫效率达 95%以上， 脱氟和脱氯效率达 95%以上， 除 尘效率达 99%。 排出石膏浆液量为 0.3〜0.6 m3/h， 由卧式螺旋卸料沉降离心 机脱水后的含水率在 50%〜60%， 经真空皮带机脱水后石膏的含水率小于 10%。 最后得到的石膏晶体颗粒粒径为 46〜100μηι。

Claims

权 利 要 求
1.一种烧结烟气湿法脱硫除尘工艺， 其特征在于包括以下步骤：
1 ) 从除尘器出来的烧结烟气经增压风机升压后， 首先进行冷却脱氟， 即 利用碱液将烟气中的 HF、 HC1气体和大颗粒烟尘基本脱除， 同时将烟温降到 80 °C以下；
2 ) 烟气进入脱硫吸收塔， 烟气中的 S02与吸收塔内的碱液反应；
3 ) 净化后的烟气进入除雾器除去烟气中的液滴， 然后被再热后从烟囱排 出。
2.如权利要求 1所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 步骤 1 ) 中的冷却脱氟过程是在一冷却脱氟器中进行的。
3.如权利要求 2所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 步骤 1 ) 中烟温是通过碱液的蒸发和冷却脱氟器中的工艺水冷却的。
4.如权利要求 3所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 所述冷 却脱氟器中产生的少量废水直接排入废水处理系统。
5.如权利要求 4所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 从冷却 脱氟器中排出的废水通过沉淀、 pH值调节等工序将废水中的重金属分离出来， 烘干的重金属污泥经磁选后回收其中的铁， 回收后的铁再返回烧结机头参与配 矿。
6.如权利要求 1所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 在步骤 2 ) 的脱硫吸收塔中， 冷却脱氟后的烟气通过吸收塔内喷气管中旋流装置的作 用， 高速旋冲入浆液池中， 烟气在浆液中被打碎并与之充分混合， 气液在高效 接触过程中完成脱硫、 除尘过程。
7.如权利要求 6所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 在步骤 2 ) 中产生的石膏浆液经两级脱水， 含水率降到 10%以下。
8.如权利要求 7所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 石膏浆 液的两级脱水分别由螺旋卸料沉降离心机或水力旋流分离器和真空皮带机完 成。
9.如权利要求 1所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 步骤 3 ) 中烟气的再加热是利用烧结余热蒸气实现的。
10. 如权利要求 1 所述的烧结烟气湿法脱硫除尘工艺， 其特征在于： 步 骤 1 ) 和 2 ) 中的碱液包括由石灰石、 熟石灰、 钠基、 镁基和铵基等一种或多 种碱性化合物配置成的水溶液或浆液。
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