WO2014172860A1 - 酸性尾气氨法烟气治理方法及装置 - Google Patents

酸性尾气氨法烟气治理方法及装置 Download PDF

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Publication number
WO2014172860A1
WO2014172860A1 PCT/CN2013/074657 CN2013074657W WO2014172860A1 WO 2014172860 A1 WO2014172860 A1 WO 2014172860A1 CN 2013074657 W CN2013074657 W CN 2013074657W WO 2014172860 A1 WO2014172860 A1 WO 2014172860A1
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Prior art keywords
absorption
absorption tower
flue gas
ammonia
spray
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PCT/CN2013/074657
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English (en)
French (fr)
Inventor
徐长香
罗静
傅国光
徐延忠
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江苏新世纪江南环保股份有限公司
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Priority to MX2015014913A priority Critical patent/MX358479B/es
Application filed by 江苏新世纪江南环保股份有限公司 filed Critical 江苏新世纪江南环保股份有限公司
Priority to EA201592029A priority patent/EA029429B1/ru
Priority to RS20180507A priority patent/RS57661B1/sr
Priority to US14/409,781 priority patent/US20160030883A1/en
Priority to HUE13882863A priority patent/HUE039257T2/hu
Priority to BR112015027018-2A priority patent/BR112015027018B1/pt
Priority to ES13882863.7T priority patent/ES2669735T3/es
Priority to PCT/CN2013/074657 priority patent/WO2014172860A1/zh
Priority to EP13882863.7A priority patent/EP2990096B1/en
Priority to CA2908484A priority patent/CA2908484C/en
Priority to PL13882863T priority patent/PL2990096T3/pl
Publication of WO2014172860A1 publication Critical patent/WO2014172860A1/zh
Priority to US14/829,905 priority patent/US9370745B2/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • B01D53/507Sulfur oxides by treating the gases with other liquids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/79Injecting reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10Inorganic absorbents
    • B01D2252/102Ammonia
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a purification technology and device for industrial flue gas such as acid tail gas (smoke gas) in a chemical (coal chemical) production process, and particularly relates to a method for removing sulfur dioxide from flue gas by using ammonia as an absorbent and by-product agricultural use.
  • Flue gas desulfurization technology and equipment for chemical fertilizers belong to the technical fields of environmental protection, electric power and chemical industry.
  • the sulfur dioxide emitted in industrial processes is an important source of acid rain and sulfur dioxide pollution.
  • the desulfurization of industrial flue gas is imperative.
  • Acid tail gas generally refers to the sulfur-containing gas produced in the chemical (coal chemical) process. After the recovery process, the sulfur, phenol, naphthalene and other substances are recovered and sent to the tail gas incinerator to fully burn the organic matter and hydrogen sulfide in the exhaust gas.
  • the exhaust gas produced in the acid tail gas is mainly sulfur dioxide and the concentration is high. The tail gas needs to be desulfurized to meet the emission requirements.
  • Coal chemical industry usually uses the Claus sulfur recovery process to remove hydrogen sulfide and recover sulfur.
  • the process of super or super-Klaus, SCOT tail gas reprocessing after the conventional secondary Claus sulfur recovery unit has the disadvantages of complicated process flow, high investment, high operating cost and high operation difficulty.
  • CN200710049014 improves the low-temperature Claus sulfur recovery method, and mixes sulfuric acid gas with air in the main combustion furnace to perform Claus reaction, and the process gas of the first tube process of the waste heat boiler is used as a reheat heat source.
  • the invention is provided with a gas/gas heat exchanger, and the heat of the first tube of the waste heat boiler of the sulfur recovery unit or the heat of the flue gas of the 60 ° C of the incinerator exit flue is used as a regenerative heat source for the subsequent reactor;
  • the four-stage reactor and the third- to fifth-stage sulfur condensing cooler are controlled by a switching valve program.
  • Each of the switching cycles has a two-bed reactor in a low-temperature adsorption state, and the one-bed reactor undergoes gradual heating and stable regeneration, and gradual pre-cooling. Stable cooling in several stages.
  • the control method is complicated and fine, and it is difficult to obtain stable control, and the desulfurization efficiency is greatly affected.
  • Small-scale organic chemical acid tail gas has been desulfurized by the sodium alkali method and the like, and has the disadvantages of high investment, high operating cost, and high operational difficulty.
  • Coal chemical enterprises that use lump coal as raw material for atmospheric pressure fixed bed gasification generally adopt the process of atmospheric pressure desulfurization. In the gas process, the atmospheric pressure (20 kPa) desulfurization tower is connected in series. At present, the domestic desulfurization of the rubber alkali solution is mostly used. Then, through the sulfur recovery device, sulfur is sulfurized to produce sulfur.
  • the desulfurization process that uses more flue gas from coal-fired boilers is the calcium method.
  • the flue gas desulfurization device has high investment and high operating cost. In particular, it needs to consume high-quality limestone resources, and the desulfurization gypsum market has a limited capacity, and the wastewater needs to be treated and discharged.
  • the sodium-alkali method is used, and the sodium-alkali resource is consumed.
  • the market demand for products such as sodium sulfate by-product is small, and it is difficult to achieve high added value, so that the operating cost is high and the reliability is poor.
  • ammonia flue gas desulfurization has high efficiency, no secondary pollution, resource recovery, short process, integration with flue gas desulfurization of factory boilers, etc., making the application of ammonia method more extensive.
  • Claus sulfur recovery + ammonia desulfurization integrated desulfurization technology is adopted, the desulfurization efficiency can reach 99.5% or more, the sulfur recovery rate is about 95%, and the by-product ammonium sulfate can be directly sold, without secondary pollution. Low investment, simple process, low operating cost and simple operation.
  • Ammonia treatment of acidity The by-product after the exhaust gas is integrated with the boiler ammonia desulfurization device, which can reduce the investment cost of the post-treatment, and the process is simpler and simpler, so that the environmental protection of the plant is intensive and beneficial to operation management.
  • the object of the present invention is to: propose an acid tail gas ammonia flue gas treatment technology and device.
  • Claus sulfur recovery + ammonia desulfurization integrated desulfurization technology which can effectively improve the desulfurization efficiency of flue gas, and can effectively control ammonia slip and aerosol generation, and at the same time, the process flow is simple, the system structure is simplified, and the operating cost is low.
  • the desulfurization rate of the device is ⁇ 95%, and the ammonia recovery rate is ⁇ 96.5 %.
  • the technical scheme of the invention is: an acid tail gas ammonia method for treating flue gas, comprising the following contents:
  • the original flue gas sulfur dioxide content can be adjusted to the appropriate absorption condition by supplementing the air, and the acid tail gas ammonia flue gas treatment in the absorption tower; the concentration of sulfur dioxide in the original flue gas of the absorption tower: 3 ⁇ 4 ⁇ 30000mg/Nm 3 ;
  • the process water is set in the inlet flue or absorption tower of the absorption tower or sprayed with ammonium sulfate solution to cool down and wash the original flue gas, so that the flue gas can achieve better desulfurization absorption process conditions;
  • the concentration of the self is increased during the spray cooling process; the ammonium sulfate solution can be concentrated until crystallization; thereby producing different concentrations of the product.
  • an oxidation section is arranged in the absorption tower, and an oxidation distributor is arranged in the oxidation section to realize oxidation of the desulfurization absorption liquid; the oxidation rate of the absorption liquid can be ensured to be greater than 98%;
  • the absorption tower is provided with an absorption section.
  • the absorption section is used to absorb desulfurization and spray absorption through the absorption liquid containing ammonia; the desulfurization rate can be guaranteed to be greater than 95%.
  • a water washing layer is arranged on the upper part of the absorption section in the absorption tower, and the water washing layer washes the absorption liquid in the flue gas to reduce the escape of the absorption liquid; at the same time, the water washing amount is controlled to maintain the concentration of the produced liquid.
  • the demister is installed in the upper part of the water washing layer in the absorption tower to control the content of the droplets in the net flue gas.
  • the flow of the acid tail gas ammonia flue gas treatment technology and device is: the acid tail gas in the original flue gas flue 8 is adjusted by the air sent by the blower 2 to adjust the sulfur dioxide concentration in the flue gas, in the absorption tower 16
  • the washing action of the cooling spray layer 15 at the inlet (or the cooling spray layer 17 sprayed with the ammonium sulfate solution in the absorption tower) is lowered to the temperature and then enters the absorption tower 16, where it is absorbed by the absorption tower through the absorption tower 13 after washing.
  • the sulfur dioxide is removed, washed and absorbed by the water washing layer 12, and the mist in the flue gas is removed by the mist eliminator 11.
  • the net flue gas after the demisting is discharged to the chimney 10 through the net flue gas flue 9.
  • the absorption liquid circulation may be one-stage circulation or two-stage circulation. If the absorption tower is required to produce a low concentration ammonium sulfate solution, only one stage of the absorption liquid circulation system can be provided. If the absorption tower is required to produce a high concentration ammonium sulfate solution or an ammonium sulfate crystal slurry, a two-stage absorption liquid circulation system is provided, and the first-stage circulation system is an absorption and oxidation cycle, and the absorption circulation pump 5 extracts the absorption liquid from the bottom of the absorption tower for absorption.
  • the tower absorbs the spray layer 13 for spraying, and the absorption liquid is contacted with the flue gas in the tower to wash and absorb the sulfur dioxide in the flue gas to form ammonium sulfite, and the absorption liquid containing ammonium sulfite is in the bottom oxidation section 4 of the absorption tower 16.
  • the secondary circulatory system is a cooling spray (concentrated crystallization) cycle, which is cooled by a washing pump.
  • the ammonium sulfate solution is pumped from the ammonium sulfate storage tank 6 into the absorption tower to cool the washing spray layer 17 and/or the inlet of the absorption tower to cool the washing layer 15, and the flue gas is cooled, and itself is evaporated to concentrate or even crystallize.
  • the product produced by the absorption tower is sent out through the ammonium sulfate discharge pump 7 for the production of products such as ammonium sulfate solid or directly used for industrial and agricultural use.
  • the main process parameters involved in the present invention are:
  • the concentration of sulfur dioxide in the original flue gas of the absorption tower is the best: 3 ⁇ 4 ⁇ 30000mg/Nm 3 ;
  • the temperature of the original flue gas in the absorption tower is absorbed into the absorption tower: " ⁇ 8(TC;
  • Absorption tower absorbs spray layer operating temperature: " ⁇ 65 °C
  • the product ammonium sulfate solution concentration is 15%.
  • the present invention may be a post-ammonia tail gas treatment process for Claus sulfur recovery (including improved Claus sulfur recovery, including boiler ammonia desulfurization unit).
  • Acid tail gas ammonia flue gas treatment device including absorption tower 16, air supply fan 2, ammonia water tank 3, absorption tower (desulfurization tower) oxidation section 4, absorption circulation pump 5, ammonium sulfate storage tank 6, ammonium sulfate discharge pump 7, Original flue gas flue 8, net flue gas flue 9, chimney 10, mist eliminator 11, water wash layer
  • the absorption tower absorbs the spray layer 13, the cooling washing pump 14, the inlet cooling washing spray layer 15, the spray pump 17, the original flue gas flue is connected to the blower 2, the absorption tower 16 inlet flue or the absorption tower is provided with process water. Or / with ammonium sulfate solution spray cooling device 15, 17; the absorption tower 16 is provided with an oxidation section 4, the oxidation section 4 is provided with an oxidation distributor to achieve oxidation of the desulfurization absorption liquid; the absorption tower is provided with an absorption section 13, the absorption section 13 The effluent distributor is used to realize the desulfurization spray absorption through the ammonia-containing absorption liquid; the oxidation section 4 is provided with the oxidation fan 1, the oxidation section 4 produces the solution output to the ammonium sulfate storage tank 6 and is sent out by the ammonium sulfate discharge pump 7;
  • the cooling spray layer 17 is sprayed by a spray spray layer with a spray coverage of more than 200%, and the spray spray layer 13 is sprayed by a spray tower or a packed tower of 2 layers to 4 layers; the coverage of each layer of spray is greater than 250%; the water washing layer 12 is placed on the absorption spray layer 13, using a packed tower type; the mist eliminator 11 is placed on the top of the absorption tower 16, and the top of the absorption tower 16 is a net flue gas flue 9 and a chimney 10.
  • the blower 2 is configured to deliver air to the original flue gas.
  • the centrifugal fan is used, and the indenter and flow rate are determined according to the original flue gas process parameters; the sulfur dioxide concentration of the treated exhaust gas is less than or equal to 30,000 mg/Nm 3 .
  • the oxidizing fan 1 is a device for the oxidation of ammonium sulfite to ammonium sulphate to supply oxidizing air, the pressure of the fan is determined according to the liquid level of the oxidizing section, the pressure is not less than 0. 05MPa. The amount of oxidizing air is greater than 150% of the theoretical value.
  • Absorption tower 1 height 20m -40m, oxidation section 4 oxidation residence time is greater than 30min and set type gas-liquid distributor such as plate or grid, absorption layer
  • Washing layer 12 The defogger empty tower gas velocity is lm/s-5m/s, and the mist eliminator 11 uses 2-3 layer baffles.
  • the present invention provides a desulfurization process scheme for an acidic tail gas, which has high efficiency, low investment, complete resource utilization, and can integrate the by-products of the ammonia tail gas treatment by the ammonia method with the boiler ammonia desulfurization device.
  • the investment cost of post-processing is reduced, and the process is simpler, which makes the environmental protection of the factory become an intensive advantage and is conducive to operation management.
  • the absorption tower inlet flue or the absorption tower is provided with process water or sprayed with ammonium sulfate solution to make the tail gas enter the tower to cool below 125 °C, and the ammonium sulfate solution with high energy consumption in the downstream can be finished.
  • Replenishing air to obtain a suitable tail gas allows the existing ammonia desulfurization process to be widely used in industrial applications.
  • the coal chemical industry adopts Claus sulfur recovery + ammonia desulfurization integrated desulfurization technology, the desulfurization efficiency can reach 99.5% or more, the sulfur recovery rate is about 95%, and the by-product ammonium sulfate can be directly sold, without secondary pollution. Low investment, simple process, low operating cost and simple operation.
  • Claus sulfur recovery + ammonia desulfurization integrated desulfurization technology the use of this technology does not require Claus sulfur recovery and improved based on Claus sulfur recovery
  • the sulfur recovery that can not be completed by Claus sulfur recovery is completed by the invention, can greatly improve the desulfurization efficiency of the flue gas, and can effectively control the ammonia escape and aerosol generation, and the process flow is simple, The system structure is simplified and the operation cost is low.
  • the desulfurization rate and ammonia recovery of the invention are both good indicators, and a positive scheme is proposed for the treatment of frequent haze and air pollution on the current land in China, and the by-products of ammonia desulfurization can be effectively utilized, and the economic value is relatively high. high.
  • the design features of the device of the invention are also concise and reliable, and at the same time, a cooling spray layer and a absorbing spray layer and a fan with adjustable air volume are provided, which is convenient for timely processing of the rear flue gas.
  • Figure 1 is a schematic view of the apparatus and flow of the present invention
  • 2 is an acid tail gas ammonia desulfurization device and a flow chart of a natural gas plant
  • Figure 3 is a coal chemical chemical Claus sulfur recovery tail gas ammonia desulfurization device and flow chart
  • Figure 4 is a chemical acid tail gas ammonia desulfurization device and a flow chart
  • Figure 5 is a flow chart of a flue gas recovery desulfurization device for a tail gas from a refinery.
  • Oxidation fan 1 air supply fan 2, ammonia water tank 3, absorption tower (desulfurization tower) oxidation section 4, absorption circulation pump 5, ammonium sulfate storage tank 6, ammonium sulfate discharge pump 7, original flue gas flue 8, net flue gas Flue 9, chimney 10, mist eliminator 11, water washing layer 12, absorption tower absorption spray layer 13, cooling washing pump 14, inlet cooling washing spray layer 15, absorption tower 16, spray pump (ammonia pump) 17, Acid tail gas inlet 18, air 19, ammonia 20, process water 21, finished sulfur ammonia or semi-finished sulfur ammonia 22.
  • the sulfur concentration of the flue gas entering the absorption tower should be determined according to factors such as product specifications, water balance, oxidation rate, and the like. Generally controlled below 30,000 mg / Nm 3 .
  • the method is to add air to the original flue gas through a blower.
  • the original flue gas generally has a temperature above 12 CTC, and the temperature should be lowered below 8 CTC before the sulfur dioxide is absorbed.
  • the method uses the process water and the ammonium sulfate solution to wash the original flue gas, and the washing layer can be arranged in the inlet flue or the tower of the absorption tower.
  • the ammonium sulfate solution lowers the temperature of the flue gas while the water in itself is evaporated, thereby increasing its concentration and even forming crystals.
  • the concentration of the product is determined according to the process water balance and needs.
  • the flue gas having a temperature below 8 CTC (of course, above 4 CTC) is absorbed in the absorption spray layer of the absorption tower in contact with the absorption liquid, and the sulfur dioxide is removed to form ammonium sulfite.
  • the method is to circulate the absorption liquid through the absorption circulation pump, and the absorbed solution is oxidized in the oxidation section of the absorption tower.
  • the lower part of the absorption spray layer or the bottom of the tower is an oxidation section.
  • the sulfur dioxide is absorbed by the absorption liquid to produce ammonium sulfite, and the absorption liquid containing ammonium sulfite enters the oxidation section of the absorption tower to be oxidized air (air, oxygen-enriched air or pure Oxygen) is oxidized to ammonium sulphate.
  • the method is to arrange an oxidizing distributor in the oxidizing section of the absorption tower, and to send oxidizing air through the oxidizing fan, and to oxidize by using a jet or the like when the concentration of the absorbing liquid is low.
  • the flue gas after the removal of sulfur dioxide entrains the liquid droplets of the absorption liquid, and the water droplets are washed on the spray layer to wash the liquid droplets.
  • the water droplets entrained in the washed flue gas are separated and removed by the above demister to reduce water consumption and impact on the surrounding environment.
  • the absorption tower is the core equipment of the process, generally cylindrical, and can also be designed into other types such as square. From bottom to top, it is generally divided into oxidation section, cooling layer (concentrated crystal section), absorption spray layer, water washing layer and mist eliminator.
  • the oxidation section can be placed at the bottom of the column or separately outside the column. Its diameter and height are determined according to the oxidation requirements. 5 ⁇ The oxidizing agent residence time is not less than 0. 5h.
  • a gas-liquid distributor is arranged in the oxidation section to ensure good contact between the gas and liquid. It can also be oxidized using equipment such as jets.
  • Cooling spray layer cooling spray layer is a spray layer that cools the original flue gas by water and ammonium sulfate solution.
  • a water sprinkler device and an ammonium sulfate sprinkling device are provided.
  • the water sprinkler device is disposed in the original flue, and the ammonium sulfate sprinkler device can be disposed on the original flue or in the absorption tower according to the product or the like.
  • the spray coverage of the cooling spray layer is greater than 200%.
  • the total amount of spray is not less than 4 times of the evaporation of the flue gas, and the ratio of liquid to gas is not less than 6 L/m 3 .
  • Washing layer The water washing layer is placed on the absorption spray layer.
  • the packed tower type is used to determine the water spray amount according to the water balance.
  • the mist eliminators are placed on top of the absorption tower and are allowed to be placed horizontally on the absorption tower exit flue.
  • the demister is generally selected as a baffle type, and it is also possible to use a structured packing as a defogger if there is no ash accumulation.
  • the average speed of the air flow in the over-flow part of the demister is 3-4. 5m/s
  • the blower is used to prepare the concentration of the original flue gas to deliver air.
  • the centrifugal fan is used, and the indenter and flow rate are determined according to the original flue gas process parameters.
  • the treated exhaust gas has a sulfur dioxide concentration of 30,000 mg/Nm 3 or less.
  • the oxidizing fan is a device for oxidizing the ammonium sulfite to the oxidized air, and the fan pressure is determined according to the oxidizing section liquid level, generally not less than 0.05 MPa.
  • the amount of oxidizing air is greater than 150% of the theoretical value.
  • Example 2 Figure 2 Acid tail gas ammonia desulfurization device of a natural gas plant
  • the total amount of acid gas flue gas 13375Nm 3 /h, flue gas temperature: 152 °C, flue gas sulfur content 31443 mg/Nm 3 , pressure 100000Pa.
  • the reactant was ammonia water at a concentration of 15%.
  • Process and equipment The process flow and equipment are shown in Figure 2. After the original flue gas is supplemented with the normal temperature air by the blower 2, the sulfur dioxide content is reduced to 22000 mg/Nm 3 and the temperature is lowered to 1 15 °C. The raw flue gas is sprayed on the inlet of the absorption tower by the process water and the ammonium sulfate solution spray layer 15 (process water 0. 2m 3 /h, ammonium sulfate solution 20 mVh). After the paint wash temperature drops to 70 ° C, it enters the absorption tower 16 for absorption. Spray.
  • the flue gas After entering the absorption tower 16, the flue gas is washed by the three absorption liquid spray layers 13 (each layer of absorption liquid 40 m 3 /h), and the sulfur dioxide is reduced to 60 mg/Nm 3 (the concentration of sulfur dioxide is 86 mg/Nm under the original flue gas condition) 3 , the desulfurization efficiency is 99.7%), the flue gas (47 °C) is washed by the water washing layer 12, and the mist eliminator 1 1 removes the mist and drops the chimney 10 to discharge.
  • the three absorption liquid spray layers 13 each layer of absorption liquid 40 m 3 /h
  • the sulfur dioxide is reduced to 60 mg/Nm 3 (the concentration of sulfur dioxide is 86 mg/Nm under the original flue gas condition) 3 , the desulfurization efficiency is 99.7%)
  • the flue gas (47 °C) is washed by the water washing layer 12, and the mist eliminator 1 1 removes the mist and drops the chimney 10 to discharge.
  • the absorption liquid after absorbing sulfur dioxide is oxidized in the oxidation section 4 at the bottom of the absorption tower by the air blasted by the oxidation fan 1 to form an ammonium sulfate solution, the ammonium sulfate solution flows into the ammonium sulfate storage tank 6, and the output part is discharged to the boiler in the factory by ammonium sulfate.
  • Preparation of ammonium sulfate in ammonia flue gas desulfurization unit Device The ammonia is pumped from the ammonia water tank 3 to the bottom of the column by the ammonia water pump 17 to adjust the pH of the absorption liquid.
  • the water washing layer 12 has a diameter of 2 m and a 200 mm corrugated packing.
  • the mist eliminator 11 has a diameter of 2m and is made of two layers of baffles.
  • Blower 2 centrifugal blower, carbon steel, rated air volume 7000 NmVh, indenter 2500Pa, two sets, one for one.
  • Ammonia tank 3 carbon steel, with a volume of 50m 3 .
  • Ammonia pump 17 stainless steel, rated flow 4m 3 /h.
  • Air blower 1 piston air compressor, flow rate 15m 3 /min, indenter 2. 0MPa, two units, one for one.
  • Absorption circulation pump 316L material, equipped with three corresponding one-layer absorption spray distributor, flow rate 40m 3 /h.
  • Figure 2 shows the acid tail gas desulfurization flow chart of the natural gas plant, which also includes the acid tail gas 23 from the natural gas system.
  • Example 3 A coal chemical Klaus sulfur recovery tail gas ammonia desulfurization device
  • the acid gas comes from the Claus sulfur recovery section of the coal chemical plant. It is produced after the hydrogen sulfide gas is recovered by two-stage Claus and then passed through the tail gas incinerator and the waste heat boiler.
  • the total amount of flue gas is 59912Nm 3 /h.
  • the temperature is 0. 02MPa.
  • the temperature of the flue gas is 165 °C, the content of S0 2 is 12600 mg/Nm 3 , the content of 0 2 is 2%, and the pressure is 0. 02MPa.
  • the reactant is 99.6% liquid ammonia.
  • the device flow chart is shown in Figure 3.
  • the raw flue gas enters the absorption tower 16 at the inlet of the absorption tower by the process water spray layer 15 (process water lm 3 /h) and the paint wash temperature drops to about 10 CTC.
  • the flue gas is washed by the washing and cooling spray layer 2 in the absorption tower (ammonium sulfate solution 120 mVh), the flue gas temperature is lowered to about 7 CTC, and the upper portion of the absorption tower 16 is washed by the three absorption liquid spray layers 13 (each The layer absorption liquid is 140 m 3 /h), the sulfur dioxide is reduced to 80 mg/Nm 3 (the desulfurization efficiency is 99.4%), the flue gas (47 °C) is washed by the water washing layer 12, and the mist eliminator 11 is defogged to the chimney. 10 emissions.
  • the absorption liquid after absorbing sulfur dioxide is oxidized in the oxidation section 4 at the bottom of the absorption tower by the air blasted by the oxidation fan 1 to form an ammonium sulfate solution, the ammonium sulfate solution flows into the ammonium sulfate storage tank 6, and the ammonium sulfate solution is pumped to the absorption tower through the cooling washing pump 14
  • the inner washing and cooling spray layer 2 washes the flue gas, and the ammonium sulfate after the washing and cooling is refluxed to the ammonium sulfate storage tank 6.
  • the concentration of ammonium sulfate in the absorption liquid of the oxidation section is controlled to be about 20%, and the ammonium sulfate concentration in the ammonium sulfate storage tank is about 45%.
  • the output part is discharged by ammonium sulfate and pumped into the ammonium sulfate evaporation crystallization unit of the factory for producing solid ammonium sulfate product.
  • Absorption tower 16 carbon steel lining glass flake coating anti-corrosion, total height 32m, tower diameter 4m.
  • a gas-liquid distributor is provided in the oxidation section 4.
  • a washing and cooling spray layer 2 is arranged in the tower, and 4 nozzles per layer.
  • an absorption spray layer consisting of three layers of spray distributors is provided, and five nozzles per layer are arranged.
  • the absorption spray layer 13 is separated from the wash cooling spray layer 2 by a gas cap.
  • the water washing layer 12 is provided with a 200 mm corrugated packing.
  • the mist eliminator 11 is made of two layers of baffles, and the material is reinforced PP.
  • Ammonia tank 3 carbon steel, with a volume of 50m 3 .
  • Ammonia pump 17 stainless steel, rated flow 4m 3 /h.
  • Oxidation fan 1 screw air compressor, flow rate 40m 3 /min, indenter 2.
  • 0MPa two units, one for one.
  • Absorption circulation pump 2605 material, equipped with three corresponding one-layer absorption spray distributor, flow rate 140m 3 /h.
  • Cooling washing pump, 2605 material two sets, one for one, flow 120m 3 /h.
  • a coal chemical Klaus sulfur recovery tail gas ammonia desulfurization flow chart also includes coal chemical Claus sulfur recovery tail gas 25, liquid ammonia 24 .
  • Embodiment 4 A chemical acid tail gas ammonia desulfurization device
  • sulfur-containing acid gas and organic waste liquid are burned in an incinerator, and heat is recovered by a waste heat boiler to produce by-product steam, which generates an acidic tail gas containing S0 2 .
  • the total amount of acid gas flue gas 11018 Nm 3 /h, flue gas temperature: 350 V, flue gas S0 2 content 2. 57%, 0 2 content 6.22%, pressure 5000 Pa.
  • the reactant was 99.6% liquid ammonia.
  • the device flow chart is shown in Figure 4.
  • the original flue gas is supplied to the room temperature air by the blower 10, and the sulfur dioxide content is lowered to 6680 mg/Nm 3 , and the temperature is lowered to 60 ° C.
  • the raw flue gas is washed at the inlet of the absorption tower by the process water spray layer 15 (process water 0. 5m 3 /h).
  • the flue gas is washed by the washing and cooling spray layer 2 in the absorption tower (ammonium sulfate solution 140 mVh), and the flue gas temperature is lowered to about 5 CTC, and the upper portion of the absorption tower 16 is washed by the three absorption liquid spray layers 13 ( Each layer of absorption liquid is 160 mVh), the sulfur dioxide is reduced to 30 mg/Nm 3 (the concentration of sulfur dioxide is 321 mg/Nm 3 under the original flue gas condition, the desulfurization efficiency is 99.6%), and the flue gas (48 °C) is washed again.
  • the 12 washing and defogger 11 is discharged after removing the mist.
  • the absorption liquid after absorbing sulfur dioxide is oxidized in the oxidation section 4 at the bottom of the absorption tower by the air blasted by the oxidation fan 1 to form an ammonium sulfate solution, the ammonium sulfate solution flows into the ammonium sulfate storage tank 6, and the ammonium sulfate solution is pumped to the absorption tower through the cooling washing pump 14
  • the inner washing and cooling spray layer 2 washes the flue gas, and the ammonium sulfate after the washing and cooling is refluxed to the ammonium sulfate storage tank 6.
  • the mother liquor returned to the ammonium sulfate storage tank 6 by solid-liquid separation is subjected to cyclic crystallization.
  • Absorption tower 16 carbon steel lining glass flake coating anti-corrosion, total height 31m, tower diameter 4. 8m.
  • a gas-liquid distributor is provided in the oxidation section 4.
  • a washing and cooling spray layer 2 is arranged in the tower, and 9 nozzles per layer.
  • an absorption spray layer 13 composed of three layers of spray distributors is provided, and 11 nozzles per layer are arranged.
  • the absorption spray layer 13 is separated from the wash cooling spray layer 2 by a gas cap.
  • the water wash layer 12 is provided with a 200 mm corrugated packing.
  • the mist eliminator 11 uses two layers of baffles and is made of PP.
  • Ammonia tank 3 carbon steel, two for one, each with a volume of 120m 3 .
  • a chemical acid tail gas ammonia desulfurization flow chart further includes a mother liquor 31 of the ammonium sulfate post-treatment system, and a flue gas discharge 27 is purified.
  • Example 5 a refinery Claus sulfur recovery tail gas ammonia desulfurization device
  • the acid gas comes from the Claus sulfur recovery section of the refinery. It is produced after the hydrogen sulfide gas is recovered by two-stage Claus and then passed through the tail gas incinerator and the waste heat boiler.
  • the total amount of flue gas is: 61221Nm 3 /h, smoke. 02MPa ⁇ Gas temperature: 160 V, smoke S0 2 content 10200 mg / Nm 3 , 0 2 content 7%, pressure 0. 02MPa.
  • the reactant is 99.6% liquid ammonia.
  • the flow chart of the device is shown in Figure 5.
  • the raw flue gas enters the absorption tower 16 after the inlet of the absorption tower is cooled by the process water spray layer 15 (process water lm 3 /h) to about 10 CTC.
  • the flue gas After entering the absorption tower 16, the flue gas is washed by the washing and cooling spray layer 2 in the absorption tower (ammonium sulfate solution 120 mVh), the flue gas temperature is lowered to about 7 CTC, and the upper portion of the absorption tower 16 is washed by the three absorption liquid spray layers 13 (each The layer absorption liquid is 140 mVh), the sulfur dioxide is reduced to 80 mg/Nm 3 (the desulfurization efficiency is 99.2%), the flue gas (46 °C) is washed by the water washing layer 12, and the mist eliminator 11 is defogged and discharged to the chimney 10 for discharge.
  • the washing and cooling spray layer 2 in the absorption tower ammonium sulfate solution 120 mVh
  • the flue gas temperature is lowered to about 7 CTC
  • the upper portion of the absorption tower 16 is washed by the three absorption liquid spray layers 13 (each The layer absorption liquid is 140 mVh)
  • the sulfur dioxide is
  • the absorption liquid after absorbing sulfur dioxide is oxidized in the oxidation tank 4 by the air blasted by the oxidation fan 1 to form an ammonium sulfate solution, and the ammonium sulfate solution flows into the ammonium sulfate solution pool 6 in the absorption tower, and the ammonium sulfate solution is pumped to the absorption tower through the cooling washing pump 14
  • the inner washing and cooling spray layer 2 washes the flue gas, and the ammonium sulfate after the washing and cooling is refluxed to the ammonium sulfate solution pool 6.
  • the concentration of ammonium sulfate in the absorption liquid of the oxidation zone is controlled to be about 20%, and the ammonium sulfate concentration in the ammonium sulfate solution pool is about 45%.
  • the output portion is pumped to the ammonium sulfate evaporation crystallization device in the factory for the production of solid ammonium sulfate product by ammonium sulfate.
  • Absorption tower 16 carbon steel lining glass flake coating anti-corrosion, total height 24m, tower diameter 4m.
  • a washing and cooling spray layer 2 is arranged in the tower, and 4 nozzles per layer.
  • an absorption spray layer consisting of three layers of spray distributors is provided, and five nozzles per layer are arranged.
  • the absorption spray layer 13 is separated from the wash cooling spray layer 2 by a gas cap.
  • the water washing layer 12 is provided with a 200 mm corrugated packing.
  • the mist eliminator 11 uses two layers of baffles and is made of PP.
  • Ammonia tank 3 carbon steel, with a volume of 50m 3 .
  • Ammonia pump 17 stainless steel, rated flow 4m 3 /h.
  • Oxidation fan 1 screw air compressor, flow rate 40m 3 /min, indenter 2.
  • 0MPa two units, one for one.
  • Absorption circulation pump 2605 material, equipped with three corresponding one-layer absorption spray distributor, flow rate 140m 3 /h.
  • Cooling washing pump, 2605 material two sets, one for one, flow 120m 3 /h.
  • Oxidation tank carbon steel lining glass scale anti-corrosion, diameter 4. 5m, height 10m; gas-liquid distributor is set in oxidation tank 4.
  • Figure 5 also includes the acid tail gas from the sulfur recovery tail gas incinerator.

Abstract

酸性尾气氨法烟气治理方法,包括以下步骤:1)控制入吸收塔尾气二氧化硫浓度:≤30000mg/Nm3;2)吸收塔入口烟道或吸收塔内设置工艺水或与硫酸铵溶液喷淋降温;3)吸收塔内设有氧化段,氧化段设置氧化分布器实现脱硫吸收液的氧化;4)吸收塔内设有吸收段,吸收段内利用吸收液分布器通过含氨的吸收液实现脱硫喷淋吸收;含氨的吸收液由氨贮槽补入;5)吸收塔内吸收段上部设置水洗涤层,水洗涤层洗涤尾气中的吸收液,降低吸收液逃逸;6)吸收塔内水洗涤层上部设置除雾器控制净化尾气中雾滴含量;用于煤化工上采用克劳斯硫回收+氨法脱硫一体化脱硫技术,可减少后处理的投资费用,流程更简捷,使工厂的环保治理形成集约化优势。

Description

酸性尾气氨法烟气治理方法及装置
技术领域
本发明涉及一种化工 (煤化工) 生产过程中酸性尾气 (烟气) 等工业烟气的净化技术和装置, 具体 涉及一种以氨为吸收剂, 脱除烟气中的二氧化硫并副产农用化肥的烟气脱硫技术及装置, 属于环保、 电 力、 化工等技术领域。
背景技术
工业过程中排放的二氧化硫是酸雨和二氧化硫污染的重要来源, 为改善环境质量、 控制二氧化硫的 排放量, 工业烟气的脱硫势在必行。
酸性尾气一般是指化工 (煤化工) 过程中产生的含硫的气体, 经回收工序将硫、 酚、 萘等等物质的 回收后再送尾气焚烧炉将尾气中的有机物、 硫化氢等充分燃烧后产生的尾气, 酸性尾气中有害成份主要 是二氧化硫且浓度较高, 尾气需进行脱硫处理才能达到排放要求。
煤化工通常采用克劳斯硫回收工艺脱除硫化氢、 回收硫磺。 为保证尾气达标排放, 在常规二级克劳 斯硫回收装置后设置超级或超优克劳斯、 SCOT尾气再处理等工艺, 存在工艺流程复杂、 投资高、 运行 成本高、 操作难度大等缺点。 如 CN200710049014 改良低温克劳斯硫磺回收方法, 在主燃烧炉内将含 硫酸气与空气混合进行克劳斯反应, 余热锅炉第一管程的过程气作为再热热源。 此发明设置有气 /气换 热器, 将硫磺回收装置余热锅炉第一管程的过程气或焚烧炉出口烟道上 6 0 0 °C烟气的热量作为后续反 应器的再生热源; 二级至四级反应器和三级至五级硫磺冷凝冷却器通过切换阀程序控制, 每个切换周期 均有两床反应器处于低温吸附态, 一床反应器经历逐步升温和稳定再生、 逐步预冷、 稳定冷却几个阶段。 控制方法复杂而精细, 不易得到稳定的控制则脱硫效率大受影响。
小型的有机化工的酸性尾气以往使用钠碱法等工艺进行脱硫处理的, 也同样存在投资高、 运行成本 高、 操作难度大等缺点。 以块煤为原料常压固定床气化的煤化工企业一般采用常压脱硫的工艺, 在煤气 流程中串入常压(20kPa)脱硫塔, 目前国内多采用栲胶碱溶液循环再生法脱硫, 再通过硫回收装置, 熔 硫析硫, 产出硫磺。
目前燃煤锅炉烟气应用较多的脱硫工艺是钙法, 烟气脱硫装置投资高、 运行成本高, 特别是需消耗 优质的石灰石资源、 副产脱硫石膏市场容量有限、 废水需进行处理排放。 在酸性尾气治理上应用较多的 是钠碱法, 需消耗钠碱资源, 所副产硫酸钠等产物市场需求少, 难以实现高附加值, 从而运行费用较高, 可靠性差。
随着氨法脱硫技术的广泛应用, 氨法脱硫的优势日益显现。 充分利用氨法烟气脱硫的效率高、 无二 次污染、 资源化回收、 流程短、 可实现与工厂锅炉烟气脱硫一体化等等优势, 使氨法的应用领域更广。 如煤化工上采用克劳斯硫回收 +氨法脱硫一体化脱硫技术, 脱硫效率可达到 99. 5%以上, 硫磺回收率约 95%, 副产硫酸铵可直接外售, 无二次污染, 投资少, 流程简单, 运行成本低, 操作简单。 氨法治理酸性 尾气后的副产物与锅炉氨法脱硫装置一体化设计, 可减少后处理的投资费用, 流程更简捷, 从而使工厂 的环保治理形成集约化优势, 有利于运行管理。
发明内容
本发明的目的是: 提出一种酸性尾气氨法烟气治理技术及装置。尤其是克劳斯硫回收 +氨法脱硫一体 化脱硫技术, 采用该技术能有效提高烟气的脱硫效率, 并能有效控制氨逃逸和气溶胶的产生, 同时工艺 流程简单、 系统结构简化、 运行成本低廉。 其装置的脱硫率≥95 %、 氨回收率≥96.5 %。
本发明的技术方案是: 酸性尾气氨法烟气治理方法及装置, 包括以下内容:
1 ) 根据原烟气 (尾气) 二氧化硫含量情况, 通过补充空气使原烟气二氧化硫含量达到适宜的吸收 条件, 在吸收塔内酸性尾气氨法烟气治理; 入吸收塔原烟气二氧化硫浓度: ¾≡30000mg/Nm3;
2 ) 吸收塔入口烟道或吸收塔内设置工艺水或与硫酸铵溶液喷淋降温, 对原烟气进行降温、 洗涤, 可使烟气达到更好的脱硫吸收的工艺条件; 当硫酸铵溶液在喷淋降温过程中自身浓度得到提高; 能够使 硫酸铵溶液浓缩直至结晶; 从而产出不同浓度的产品。
3 ) 吸收塔内设有氧化段, 氧化段设置氧化分布器实现脱硫吸收液的氧化; 可以保证吸收液氧化率 大于 98%;
4 ) 吸收塔内设有吸收段, 吸收段内利用吸收液分布器通过含氨的吸收液实现脱硫喷淋吸收; 可以 保证脱硫率大于 95%。
5 ) 吸收塔内吸收段上部设置水洗涤层, 水洗涤层洗涤烟气中的吸收液, 降低吸收液逃逸; 同时控 制水洗涤量, 保持产出液的浓度。
6 ) 吸收塔内水洗涤层上部设置除雾器控制净烟气中雾滴含量。
本发明的工艺流程,所述酸性尾气氨法烟气治理技术及装置的流程为: 酸性尾气在原烟气烟道 8中通 过送风机 2送来的空气调整烟气中二氧化硫浓度, 在吸收塔 16的入口处降温喷淋层 15 (或与吸收塔内硫酸 铵溶液喷淋的降温喷淋层 17 ) 的洗涤作用下降温后进入吸收塔 16, 在吸收塔 16内经吸收塔吸收喷淋层 13 洗涤后将二氧化硫脱除, 再经水洗层 12洗涤吸收, 又经除雾器 11除去烟气中的雾滴, 除雾后的净烟气通 过净烟气烟道 9去烟囱 10排放。
降温时采用补充空气降温、 用工艺水或与硫酸铵溶液降温。
进一步的, 吸收液循环可一级循环也可两级循环。 如果需吸收塔产出低浓度硫酸铵溶液时可以只设 置一级吸收液循环系统。 如果需吸收塔产出高浓度硫酸铵溶液或硫酸铵结晶浆液时设置两级吸收液循环 系统, 一级的循环系统为吸收、 氧化循环, 吸收循环泵 5将吸收液从吸收塔底抽出送吸收塔吸收喷淋层 13进行喷淋, 吸收液在塔内与烟气接触将烟气中的二氧化硫洗涤吸收下来, 生成亚硫酸铵, 含亚硫酸铵 的吸收液在吸收塔 16底氧化段 4中与氧化风机 1送来的氧化空气接触后亚硫酸铵氧化成硫酸铵, 所需氨由 氨贮槽 3补入; 二级的循环系统为降温喷淋(浓缩结晶)循环, 通过降温洗涤泵将硫酸铵溶液自硫酸铵贮 槽 6泵入吸收塔内降温洗涤喷淋层 17和 /或吸收塔入口降温洗涤层 15, 将烟气进行降温, 自身得到蒸发浓 缩甚至产生结晶。 吸收塔产出的产品通过硫酸铵排出泵 7外送, 供生产硫酸铵固体等产品或直接为工农业 使用。 本发明涉及的主要工艺参数为:
入吸收塔原烟气二氧化硫浓度最佳: ¾≡30000mg/Nm3 ;
入吸收塔吸收喷淋层原烟气温度最佳: 《≡8(TC;
吸收塔吸收喷淋层操作温度: 《≡65 °C
吸收液温度: 《≡65 °C
吸收塔空塔气速: 1. 5 m/s-4m/s
降温洗涤液气比: 《≡6 L/m3
吸收喷淋液气比: 1 L/m3-15 L/m3
产品硫酸铵溶液浓度 15%。
本发明可以是克劳斯硫回收 (包括改良的克劳斯硫回收, 也包括锅炉氨法脱硫装置) 的后道氨法尾 气处理工艺。
酸性尾气氨法烟气治理装置, 包括吸收塔 16, 送风风机 2、 氨水罐 3、 吸收塔 (脱硫塔) 氧化段 4、 吸收循环泵 5、 硫酸铵储槽 6、 硫酸铵排出泵 7、 原烟气烟道 8、 净烟气烟道 9、 烟囱 10、 除雾器 11、 水洗层
12、 吸收塔吸收喷淋层 13、 降温洗涤泵 14、入口降温洗涤喷淋层 15、喷淋泵 17, 原烟气烟道连接送风机 2, 吸收塔 16入口烟道或吸收塔内设置工艺水或 /与硫酸铵溶液喷淋降温装置 15、 17; 吸收塔 16内设有氧化 段 4, 氧化段 4设置氧化分布器实现脱硫吸收液的氧化; 吸收塔内设有吸收段 13, 吸收段 13内利用吸收液 分布器通过含氨的吸收液实现脱硫喷淋吸收; 氧化段 4配置有氧化风机 1、氧化段 4产出溶液输出至硫酸铵 储槽 6并由硫酸铵排出泵 7送出装置;
降温喷淋层 17是喷淋覆盖率大于 200%的降温喷淋层喷淋,吸收喷淋层 13采用喷淋塔或填料塔的 2层 -4 层喷淋; 每层喷淋的覆盖率大于 250% ; 水洗层 12置于吸收喷淋层 13上, 采用填料塔型式; 除雾器 11置于 吸收塔 16顶, 吸收塔 16顶为净烟气烟道 9和烟囱 10。
送风机 2为原烟气配制浓度输送空气的, 采用离心风机, 压头与流量根据原烟气工艺参数确定; 使 处理的废气的二氧化硫浓度小于等于 30000mg/Nm3
氧化风机 1是为将亚硫酸铵氧化成硫酸铵供给氧化空气的设备, 根据氧化段液位确定风机压力, 压 力不小于 0. 05MPa。 氧化空气量大于理论值的 150%。
吸收塔 1高 20m -40m, 氧化段 4氧化停留时间大于 30min并设置板式或格栅等型式气液分布器, 吸收层
13、 水洗层 12除雾器空塔气速 lm/s-5m/s, 除雾器 11采用 2-3层折流板。
本发明的有益效果: 本发明提供了针对酸性尾气的脱硫工艺方案, 效率高, 投资省, 完全资源化, 且可以将氨法治理酸性尾气后的副产物与锅炉氨法脱硫装置一体化设计, 减少了后处理的投资费用, 流 程更简捷, 从而使工厂的环保治理形成集约化优势, 有利于运行管理。
其中吸收塔入口烟道或吸收塔内设置工艺水或与硫酸铵溶液喷淋使尾气入塔降温至 125 °C以下, 又 能后道能耗高的硫酸铵溶液进行成品化处理。 补充空气得到适合的尾气使现有氨法脱硫工艺得到广泛的 工业化应用。 使如煤化工采用克劳斯硫回收 +氨法脱硫一体化脱硫技术, 脱硫效率可达到 99. 5%以上, 硫 磺回收率约 95%, 副产硫酸铵可直接外售, 无二次污染, 投资少, 流程简单, 运行成本低, 操作简单。 尤其是克劳斯硫回收 +氨法脱硫一体化脱硫技术,采用该技术无须克劳斯硫回收及基于克劳斯硫回收改进 的各种复杂而谨慎的控制, 克劳斯硫回收未能完成的硫回收由本发明完成, 能大大有效提高烟气的脱硫 效率, 并能有效控制氨逃逸和气溶胶的产生, 同时工艺流程简单、 系统结构简化、 运行成本低廉。 本发 明脱硫率和氨回收均是一个很好的指标, 对现在的中国大地上频繁出现的雾霾大气污染的治理提出一个 积极的方案, 且氨法脱硫的副产品均可以有效利用, 经济价值较高。 本发明装置的设计特征亦简明可靠, 同时设有降温喷淋层和吸收喷淋层以及可调风量的风机, 便于及时处理后道烟气。
附图说明
图 1是本发明装置和流程示意图;
图 2为某天然气工厂的酸性尾气氨法脱硫装置及流程图;
图 3为某煤化工克劳斯硫回收尾气氨法脱硫装置及流程图;
图 4为化工酸性尾气氨法脱硫装置及流程图;
图 5为某炼油厂克劳斯硫回收尾气氨法脱硫装置及流程图。
氧化风机 1、 送风风机 2、 氨水罐 3、 吸收塔 (脱硫塔) 氧化段 4、 吸收循环泵 5、 硫酸铵储槽 6、 硫酸 铵排出泵 7、 原烟气烟道 8、 净烟气烟道 9、 烟囱 10、 除雾器 11、 水洗层 12、 吸收塔吸收喷淋层 13、 降温洗 涤泵 14、 入口降温洗涤喷淋层 15、 吸收塔 16、 喷淋泵 (氨水泵) 17、 酸性尾气进口 18、 空气 19、 氨 20、 工艺水 21、 成品硫氨外送或半成品硫氨 22。
具体实施方式
本发明工艺可分为三大步骤:
A、 烟气浓度调节
进吸收塔的烟气含硫浓度需根据产品规格、水平衡、氧化速率等等因素确定。一般控制在 30000mg/Nm3 以下。 方法是通过送风机向原烟气中补充空气。
B、 原烟气降温、 吸收液浓缩 (结晶)
原烟气一般温度在 12CTC以上, 进行二氧化硫吸收前应把温度降到 8CTC以下。 方法是利用工艺水、 硫酸铵溶液对原烟气进行洗涤, 可以在吸收塔入口烟道或塔内设置洗涤层。 硫酸铵溶液降低烟气温度的 同时自身中的水分得到蒸发, 从而提高了自身的浓度, 甚至可以形成结晶, 产品的浓度根据工艺水平衡 及需要确定。
C、 二氧化硫吸收
温度在 8CTC以下(当然在 4CTC以上)的烟气在吸收塔的吸收喷淋层与吸收液接触进行吸收反应, 二 氧化硫被脱除, 生成亚硫酸铵。 方法是通过吸收循环泵进行吸收液循环, 吸收后的溶液进吸收塔的氧化 段进行氧化。
D、 亚硫酸铵氧化
吸收喷淋层的下部或塔底为氧化段, 二氧化硫被吸收液吸收后产生亚硫酸铵,含亚硫酸铵的吸收液 进吸收塔的氧化段被氧化空气 (可采用空气、 富氧空气或纯氧气) 氧化为硫酸铵。 方法是在吸收塔的氧 化段设置氧化分布器, 通过氧化风机送入氧化空气, 吸收液浓度低时也可采用射流等方式进行氧化。
F、 烟气的水洗、 除雾
脱除二氧化硫后的烟气夹带了吸收液液滴,在喷淋层上面用水进行洗涤将吸收液液滴洗涤下来,水 洗后的烟气夹带的水液滴再由上面的除雾器进行分离脱除, 以减少水的消耗和对周边环境的影响。 本发明的主要设备特征:
1 ) 吸收塔
吸收塔是本工艺的核心设备, 一般为圆柱型, 也可设计成方型等其它型式。 从下到上一般分为氧化 段、 降温洗涤层 (浓缩结晶段) 、 吸收喷淋层、 水洗层、 除雾器几个部分。 吸收塔烟气流通部分空塔气 速: 1. 5 m/s-4m/s。
A ) 氧化段
氧化段可置于塔底部, 也可单独置于塔外。 其直径与高度根据氧化要求确定。 一般要求氧化液停留 时间不小于 0. 5h。
氧化段内设置气液分布器, 保证气液良好接触。 也可采用射流等设备进行氧化。
B ) 降温喷淋层 降温喷淋层是通过水、 硫酸铵溶液将原烟气进行降温的喷淋层, 一般设置一个水 喷淋装置和一个硫酸铵喷淋装置。 水喷淋装置设置在原烟道内, 硫酸铵喷淋装置根据产品等情况既可设 置在原烟道上也可设置在吸收塔内。 降温喷淋层喷淋覆盖率大于 200%。 喷淋总量不小于烟气蒸发量的 4 倍, 且液气比不小于 6 L/m3
C ) 吸收喷淋层 吸收喷淋层设置在塔的中上部, 一般采用喷淋塔型式, 也可采用喷淋塔与填料 塔相结合的型式, 根据烟气二氧化硫浓度选择 2层 -4层喷淋。 每层喷淋的覆盖率大于 250%。
D ) 水洗层 水洗层置于吸收喷淋层上, 采用填料塔型式, 根据水平衡确定喷水量。
E ) 除雾器 除雾器置于吸收塔顶, 允许水平放置的也可置于吸收塔出口烟道上。 除雾器一般选 用折流板型式, 无积灰可能的也可采用规整填料作除雾器。 一般除雾器过流部分空塔气速 3-4. 5m/s
2 ) 送风机
送风机为原烟气配制浓度输送空气的, 一般采用离心风机, 压头与流量根据原烟气工艺参数确定。 使处理的废气的二氧化硫浓度小于等于 30000mg/Nm3
3 ) 氧化风机
氧化风机是为将亚硫酸铵氧化成硫酸铵供给氧化空气的设备, 根据氧化段液位确定风机压力, 一般 不小于 0. 05MPa。 氧化空气量大于理论值的 150%。
实施例 2: 图 2某天然气工厂的酸性尾气氨法脱硫装置
酸性气体烟气总量: 13375Nm3/h, 烟气温度: 152 °C, 烟气含硫量 31443 mg/Nm3, 压力 100000Pa。 反应剂为氨水, 浓度为 15%。
工艺流程与装置: 工艺流程与装置见附图 2。原烟气通过送风机 2补充常温空气后二氧化硫含量降至 22000 mg/Nm3, 温度降到 1 15 °C。 原烟气在吸收塔入口被工艺水及硫酸铵溶液喷淋层 15 (工艺水 0. 2m3/h、 硫酸铵溶液 20 mVh) 洗漆温度降到 70°C后进入吸收塔 16进行吸收液喷淋。 进入吸收塔 16后烟气被三个吸 收液喷淋层 13洗涤 (每层吸收液 40 m3/h ) , 二氧化硫降到 60 mg/Nm3 (折原烟气条件下二氧化硫浓度为 86 mg/Nm3, 脱硫效率 99. 7%) , 烟气 (47 °C ) 再经水洗层 12洗涤、 除雾器 1 1除雾滴去烟囱 10排放。
吸收二氧化硫后的吸收液在吸收塔底部氧化段 4中被氧化风机 1鼓入的空气氧化生成硫酸铵溶液, 硫酸铵溶液流入硫酸铵贮槽 6, 产出部分用硫酸铵排出泵送工厂内锅炉氨法烟气脱硫装置的硫酸铵制备 装置。 氨自氨水槽 3用氨水泵 17泵入塔底部调节吸收液 pH。
装置主要特征:
吸收塔 16, 316L材质, 总高 29m。
氧化段 4直径 4m,设置格栅式气液分布器, 吸收喷淋层 13直径 2m,设三层喷淋分布器,每层 3只喷头。 水洗层 12直径 2m, 设 200mm波紋填料。
除雾器 11直径 2m, 采用两层折流板, 材质增强 PP。
送风机 2, 离心鼓风机, 碳钢材质, 额定风量 7000 NmVh, 压头 2500Pa, 配置两台, 一用一备。 氨 水贮槽 3, 碳钢材质, 体积为 50m3
氨水泵 17, 不锈钢材质, 额定流量 4m3/h。
送风机 1, 活塞式空压机, 流量 15m3/min, 压头 2. 0MPa, 配置两台, 一用一备。
吸收循环泵, 316L材质, 配置三台各对应一层吸收喷淋分布器, 流量 40m3/h。
运行参数与结果: 15%氨水消耗 1531kg/h,产出 25%的硫酸铵溶液 3460kg/h, 氨回收率 97%。
装置净烟气二氧化硫降到 60 mg/Nm3 (折原烟气条件下二氧化硫浓度为 86 mg/Nm3 ),脱硫效率 99. 7%。 图 2天然气工厂的酸性尾气脱硫流程图中, 还包括天然气系统来的酸性尾气 23, 氨水 24。
实施例 3: 某煤化工克劳斯硫回收尾气氨法脱硫装置
酸性气体来自煤化工装置的克劳斯硫回收工段, 是硫化氢气体经两级克劳斯进行硫回收后再经尾气 焚烧炉和余热锅炉后产生的, 烟气总量: 59912Nm3/h, 烟气温度: 165 °C, 烟气 S02含量 12600 mg/Nm3, 02含量 2%, 压力 0. 02MPa。 反应剂为 99. 6%液氨。
流程: 装置流程图见附图 3。 原烟气在吸收塔入口被工艺水喷淋层 15 (工艺水 lm3/h ) 洗漆温度降到 10CTC左右后进入吸收塔 16。 进入吸收塔 16后烟气被吸收塔内洗涤降温喷淋层 2洗涤 (硫酸铵溶液 120 mVh) , 烟气温度降至 7CTC左右进入吸收塔 16上部被三个吸收液喷淋层 13洗涤 (每层吸收液 140 m3/h) , 二氧化硫降到 80 mg/Nm3 (脱硫效率 99. 4% ) , 烟气 (47 °C ) 再经水洗层 12洗涤、 除雾器 11除雾滴去烟囱 10排放。
吸收二氧化硫后的吸收液在吸收塔底部氧化段 4中被氧化风机 1鼓入的空气氧化生成硫酸铵溶液, 硫酸铵溶液流入硫酸铵贮槽 6,硫酸铵溶液通过降温洗涤泵 14泵至吸收塔内洗涤降温喷淋层 2洗涤烟气, 洗涤降温后的硫酸铵回流到硫酸铵贮槽 6。
控制氧化段吸收液中硫酸铵浓度 20%左右,硫酸铵贮槽硫酸铵浓度 45%左右, 产出部分用硫酸铵排出 泵送工厂内硫酸铵蒸发结晶装置供生产固体硫酸铵产品。
液氨自氨槽 3用氨泵 17泵 (气温高时或靠氨槽自身的压力) 入塔调节吸收液 pH。
装置主要特征:
吸收塔 16, 碳钢衬玻璃鳞片涂料防腐, 总高 32m, 塔径 4m。
氧化段 4中设置气液分布器。 塔内设置一层洗涤降温喷淋层 2, 每层 4只喷头。 在洗涤降温喷淋层 2 上部设由三层喷淋分布器组成的吸收喷淋层 13, 每层 5只喷头。 吸收喷淋层 13与洗涤降温喷淋层 2用气帽 隔开。
水洗层 12设 200mm波紋填料。 除雾器 11采用两层折流板, 材质增强 PP。
氨水贮槽 3, 碳钢材质, 体积为 50m3
氨水泵 17, 不锈钢材质, 额定流量 4m3/h。
氧化风机 1, 螺杆式空压机, 流量 40m3/min, 压头 2. 0MPa, 配置两台, 一用一备。
吸收循环泵, 2605材质, 配置三台各对应一层吸收喷淋分布器, 流量 140m3/h。
降温洗涤泵, 2605材质, 配置两台, 一用一备, 流量 120m3/h。
运行参数与结果: 99. 6%液氨消耗4121¾/11,产出45%的硫酸铵溶液34381¾/11, 氨回收率 97. 1%。 装置 净烟气二氧化硫降到 80 mg/Nm3, 脱硫效率 99. 4%。
图 3 中某煤化工克劳斯硫回收尾气氨法脱硫流程图还包括煤化工克劳斯硫回收尾气 25、 液氨 24。 实施例 4、 某化工酸性尾气氨法脱硫装置
某化工项目产生含硫的酸性气、 有机废液在焚烧炉内燃烧, 热量被余热锅炉回收副产蒸汽, 所生成 含 S02的酸性尾气。 此酸性气体烟气总量: 11018Nm3/h, 烟气温度: 350 V, 烟气 S02含量 2. 57%, 02含量 6. 22%, 压力 5000Pa。
反应剂为 99. 6%液氨。
流程: 装置流程图见附图 4。 原烟气通过送风机 10补充常温空气后二氧化硫含量降至 6680 mg/Nm3, 温度降到 60°C。 原烟气在吸收塔入口被工艺水喷淋层 15 (工艺水 0. 5m3/h ) 洗涤温度。 并进入吸收塔 16后 烟气被吸收塔内洗涤降温喷淋层 2洗涤 (硫酸铵溶液 140 mVh) , 烟气温度降至 5CTC左右进入吸收塔 16上 部被三个吸收液喷淋层 13洗涤 (每层吸收液 160 mVh) , 二氧化硫降到 30 mg/Nm3 (折原烟气条件下二氧 化硫浓度为 321 mg/Nm3, 脱硫效率 99. 6% ) , 烟气 (48 °C ) 再经水洗层 12洗涤、 除雾器 11除雾滴后排放。
吸收二氧化硫后的吸收液在吸收塔底部氧化段 4中被氧化风机 1鼓入的空气氧化生成硫酸铵溶液, 硫酸铵溶液流入硫酸铵贮槽 6,硫酸铵溶液通过降温洗涤泵 14泵至吸收塔内洗涤降温喷淋层 2洗涤烟气, 洗涤降温后的硫酸铵回流到硫酸铵贮槽 6。
控制氧化段吸收液中硫酸铵浓度 30%左右, 控制硫酸铵贮槽硫酸铵固含量 10%左右, 产出部分用硫酸 铵排出泵送工厂内硫酸铵后处理系统进行固液分离, 后处理系统固液分离产生的母液回硫酸铵贮槽 6进 行循环结晶。
液氨自氨槽 3用氨泵 17泵 (气温高时或靠氨槽自身的压力) 入塔调节吸收液 pH。
装置主要特征:
吸收塔 16, 碳钢衬玻璃鳞片涂料防腐, 总高 31m, 塔径 4. 8m。 氧化段 4中设置气液分布器。
塔内设置一层洗涤降温喷淋层 2, 每层 9只喷头。 在洗涤降温喷淋层 2上部设由三层喷淋分布器组 成的吸收喷淋层 13,每层 11只喷头。吸收喷淋层 13与洗涤降温喷淋层 2用气帽隔开。水洗层 12设 200mm 波紋填料。 除雾器 11采用两层折流板, 材质增强 PP。
氨贮槽 3, 碳钢材质, 两只一用一备, 每只体积为 120m3
氨泵 17, 不锈钢材质, 额定流量 lm3/h。 氧化风机 1, 罗茨式空压机, 流量 50m3/min, 压头 0. 15MPa, 配置两台, 一用一备。 吸收循环泵, 2605材质, 配置三台各对应一层吸收喷淋分布器, 流量 160m3/h。 降 温洗涤泵, 2605材质, 配置两台, 一用一备, 流量 140m3/h。 运行参数与结果: 99. 6%液氨消耗 431kg/h,产出固体硫酸铵 1618kg/h, 氨回收率 97. 1%。
装置净烟气二氧化硫降到 30 mg/Nm3, 折原烟气条件下二氧化硫浓度为 321 mg/Nm3, 脱硫效率 99. 6%。 图 4中某化工酸性尾气氨法脱硫流程图还包括硫酸铵后处理系统母液 31、 净化烟气排出 27。
实施例 5、 某炼油厂克劳斯硫回收尾气氨法脱硫装置
酸性气体来自炼油装置的克劳斯硫回收工段, 是硫化氢气体经两级克劳斯进行硫回收后再经尾气焚 烧炉和余热锅炉后产生的, 烟气总量: 61221Nm3/h, 烟气温度: 160 V, 烟气 S02含量 10200 mg/Nm3, 02含 量 7%, 压力 0. 02MPa。 反应剂为 99. 6%液氨。
流程: 装置流程图见附图 5某煤化工克劳斯硫回收尾气氨法脱硫流程图。 原烟气在吸收塔入口被工 艺水喷淋层 15 (工艺水 lm3/h ) 洗涤温度降到 10CTC左右后开始进入吸收塔 16。 进入吸收塔 16后烟气被吸 收塔内洗涤降温喷淋层 2洗涤 (硫酸铵溶液 120 mVh) , 烟气温度降至 7CTC左右进入吸收塔 16上部被三个 吸收液喷淋层 13洗涤 (每层吸收液 140 mVh) , 二氧化硫降到 80 mg/Nm3 (脱硫效率 99. 2% ) , 烟气 (46 °C ) 再经水洗层 12洗涤、 除雾器 11除雾滴去烟囱 10排放。
吸收二氧化硫后的吸收液在氧化槽 4中被氧化风机 1鼓入的空气氧化生成硫酸铵溶液, 硫酸铵溶液 流入吸收塔内硫酸铵溶液池 6,硫酸铵溶液通过降温洗涤泵 14泵至吸收塔内洗涤降温喷淋层 2洗涤烟气, 洗涤降温后的硫酸铵回流到硫酸铵溶液池 6。
控制氧化段吸收液中硫酸铵浓度 20%左右,硫酸铵溶液池硫酸铵浓度 45%左右, 产出部分用硫酸铵排 出泵送工厂内硫酸铵蒸发结晶装置供生产固体硫酸铵产品。
液氨自氨槽 3用氨泵 17泵 (气温高时或靠氨槽自身的压力) 入塔调节吸收液 pH。
装置主要特征:
吸收塔 16, 碳钢衬玻璃鳞片涂料防腐, 总高 24m, 塔径 4m。
塔内设置一层洗涤降温喷淋层 2, 每层 4只喷头。在洗涤降温喷淋层 2上部设由三层喷淋分布器组成的 吸收喷淋层 13, 每层 5只喷头。 吸收喷淋层 13与洗涤降温喷淋层 2用气帽隔开。
水洗层 12设 200mm波紋填料。
除雾器 11采用两层折流板, 材质增强 PP。
氨水贮槽 3, 碳钢材质, 体积为 50m3
氨水泵 17, 不锈钢材质, 额定流量 4m3/h。
氧化风机 1, 螺杆式空压机, 流量 40m3/min, 压头 2. 0MPa, 配置两台, 一用一备。
吸收循环泵, 2605材质, 配置三台各对应一层吸收喷淋分布器, 流量 140m3/h。
降温洗涤泵, 2605材质, 配置两台, 一用一备, 流量 120m3/h。
氧化槽, 碳钢衬玻璃鳞片防腐, 直径 4. 5m, 高 10m; 氧化槽 4中设置气液分布器。
运行参数与结果:
99. 2%液氨消耗 341kg/h,产出 45%的硫酸铵溶液 2840kg/h, 氨回收率 97. 3%。
装置净烟气二氧化硫降到 80 mg/Nm3, 脱硫效率 99. 2%。 图 5中还包括硫回收尾气焚烧炉来的酸性尾气
30。

Claims

权利要求书
1、 酸性尾气氨法烟气治理方法, 其特征是, 包括以下步骤:
1 ) 根据原尾气二氧化硫含量情况, 通过补充空气使原尾气二氧化硫含量达到适宜的吸 收条件; 入吸收塔尾气二氧化硫浓度: ¾≡30000mg/Nm3;
2 ) 吸收塔入口烟道或吸收塔内设置工艺水或与硫酸铵溶液喷淋降温, 对原尾气进行降 温、 洗涤; 当使用硫酸铵溶液喷淋降温过程中硫酸铵自身浓度得到提高;
3 ) 吸收塔内设有氧化段, 氧化段设置氧化分布器实现脱硫吸收液的氧化;
4 ) 吸收塔内设有吸收段, 吸收段内利用吸收液分布器通过含氨的吸收液实现脱硫喷淋 吸收; 含氨的吸收液由氨贮槽补入;
5 ) 吸收塔内吸收段上部设置水洗涤层, 水洗涤层洗涤尾气中的吸收液, 降低吸收液逃 逸;
6) 吸收塔内水洗涤层上部设置除雾器控制净化尾气中雾滴含量;
所述酸性尾气氨法烟气治理的流程为: 酸性尾气在原烟气烟道中通过送风机送来的空气 调整烟气中二氧化硫浓度, 在吸收塔的入口处降温喷淋层或与吸收塔内硫酸铵溶液喷淋的降 温喷淋层的洗涤作用下降温后进入吸收塔, 在吸收塔内经吸收塔吸收喷淋层洗涤后将二氧化 硫脱除, 再经水洗层洗涤吸收, 又经除雾器除去烟气中的雾滴, 除雾后的净化尾气通过净烟 气烟道去烟囱排放。
2、 根据权利要求 1所述的酸性尾气氨法烟气治理方法, 其特征是, 吸收液循环为一级循 环或两级循环; 二级的循环系统为降温喷淋的浓缩结晶循环, 通过降温洗涤泵将硫酸铵溶液 自硫酸铵贮槽泵入吸收塔内降温洗涤喷淋层和 /或吸收塔入口降温洗涤层, 将烟气进行降温, 自身得到蒸发浓缩甚至产生结晶。
3、根据权利要求 1所述的酸性尾气氨法烟气治理方法, 其特征是, 入吸收塔吸收喷淋层 原烟气温度: 80。C ; 吸收塔吸收喷淋层操作温度: ¾≡65°C ; 吸收液温度: ¾≡65°C。
4、根据权利要求 3所述的酸性尾气氨法烟气治理方法,其特征是, 吸收塔空塔气速: 1. 5 m/s-4m/s ; 降温洗涤液气比: ¾≡6 L/m3; 吸收喷淋液气比: 1 L/m3_15 L/m3; 产品硫酸铵溶液 浓度 15%。
5、 根据权利要求 1-4之一所述的酸性尾气氨法烟气治理方法, 其特征是用于克劳斯硫回 收或改良的克劳斯硫回收的后道氨法尾气处理工艺; 降温时采用补充空气降温、 用工艺水或 与硫酸铵溶液降温。
6、酸性尾气氨法烟气治理装置, 其特征是包括吸收塔(16)、送风机(2)、氨水罐(3)、 吸收塔氧化段 (4) 、 吸收循环泵 (5) 、 硫酸铵储槽 (6) 、 硫酸铵排出泵 (7) 、 原烟气烟 道 (8) 、 净烟气烟道 (9) 、 烟囱 (10) 、 除雾器 (11) 、 水洗层 (12) 、 吸收塔吸收喷淋 层 (13) 、 降温洗涤泵 (14) 、 入口降温洗涤喷淋层 (15) 、 喷淋泵 (17) , 原烟气烟道连 接送风机(2) , 吸收塔入口烟道或吸收塔内设置工艺水或 /与硫酸铵溶液喷淋降温装置; 吸 收塔 (16) 内设有氧化段 (4) , 氧化段 (4) 设置氧化分布器实现脱硫吸收液的氧化; 吸收 塔 (16) 内设有吸收段, 吸收段 (16) 内利用吸收液分布器通过含氨的吸收液实现脱硫喷淋 吸收; 氧化段 (4) 配置有氧化风机 (1) ; 氧化段 (4) 产出溶液输出至硫酸铵储槽 (6) 并 由硫酸铵排出泵(7)送出装置; 降温喷淋层是喷淋覆盖率大于 200%的降温喷淋层喷淋, 吸收 喷淋层 13采用喷淋塔或填料塔的 2层 -4层喷淋; 每层喷淋的覆盖率大于 250%。
7、 根据权利要求 6所述的酸性尾气氨法烟气治理装置, 其特征是水洗层 (12) 置于吸收 喷淋层 (13) 上, 采用填料塔型式; 除雾器置于吸收塔顶, 吸收塔顶为净烟气烟道和烟囱。
8、根据权利要求 6所述的酸性尾气氨法烟气治理装置, 其特征是送风机为原烟气配制浓 度输送空气的, 采用离心风机, 压头与流量根据原烟气工艺参数确定; 使处理的废气的二氧 化硫浓度小于等于 30000mg/Nm3
9、根据权利要求 6所述的酸性尾气氨法烟气治理装置, 其特征是氧化风机为将亚硫酸铵 氧化成硫酸铵供给氧化空气的设备, 根据氧化段液位确定风机压力, 压力不小于 0.05Mpa, 氧化空气量大于理论值的 150%。
10、根据权利要求 6或 7所述的酸性尾气氨法烟气治理装置,其特征是吸收塔高 20m -40m, 氧化段 4氧化停留时间大于 30min并设置板式或格栅等型式气液分布器, 吸收喷淋层(13) 、 水洗层 (12) 除雾器空塔气速 lm/s-5m/s, 除雾器 (11) 采用 2-3层折流板。
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CN110354677A (zh) * 2019-07-04 2019-10-22 柳州钢铁股份有限公司 一种烧结、球团机头烟气排放净化系统
CN110354677B (zh) * 2019-07-04 2024-02-27 柳州钢铁股份有限公司 一种烧结、球团机头烟气排放净化系统

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EP2990096A1 (en) 2016-03-02
BR112015027018A2 (pt) 2017-07-25
US20160030883A1 (en) 2016-02-04
EP2990096A4 (en) 2016-04-13
EA029429B1 (ru) 2018-03-30
BR112015027018B1 (pt) 2019-06-04
MX2015014913A (es) 2016-06-02
MX358479B (es) 2018-08-22
CA2908484A1 (en) 2014-10-30
EP2990096B1 (en) 2018-03-21
EA201592029A1 (ru) 2016-02-29
ES2669735T3 (es) 2018-05-29
CA2908484C (en) 2019-09-24

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