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 PDFInfo
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- 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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- WIPO (PCT)
- Prior art keywords
- absorption
- absorption tower
- flue gas
- ammonia
- spray
- Prior art date
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 182
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003546 flue gas Substances 0.000 title claims abstract description 120
- 239000007789 gas Substances 0.000 title claims abstract description 99
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 80
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 9
- 238000010521 absorption reaction Methods 0.000 claims abstract description 229
- 239000007921 spray Substances 0.000 claims abstract description 113
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 96
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000007788 liquid Substances 0.000 claims abstract description 78
- 230000003647 oxidation Effects 0.000 claims abstract description 70
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 70
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 69
- 230000023556 desulfurization Effects 0.000 claims abstract description 69
- 238000005406 washing Methods 0.000 claims abstract description 67
- 238000001816 cooling Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000011084 recovery Methods 0.000 claims abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- 239000011593 sulfur Substances 0.000 claims abstract description 37
- 239000003595 mist Substances 0.000 claims abstract description 21
- 238000003860 storage Methods 0.000 claims abstract description 17
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 95
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 95
- 239000002253 acid Substances 0.000 claims description 33
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 24
- 239000003245 coal Substances 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 235000010269 sulphur dioxide Nutrition 0.000 description 38
- 230000001590 oxidative effect Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- 229910000975 Carbon steel Inorganic materials 0.000 description 9
- 239000010962 carbon steel Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000779 smoke Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000001166 ammonium sulphate Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000004291 sulphur dioxide Substances 0.000 description 3
- AQGDXJQRVOCUQX-UHFFFAOYSA-N N.[S] Chemical compound N.[S] AQGDXJQRVOCUQX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- AWADHHRPTLLUKK-UHFFFAOYSA-N diazanium sulfuric acid sulfate Chemical compound [NH4+].[NH4+].OS(O)(=O)=O.[O-]S([O-])(=O)=O AWADHHRPTLLUKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- 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
- B01D53/79—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
- B01D2252/102—Ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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.
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Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
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CA2908484A CA2908484C (en) | 2013-04-24 | 2013-04-24 | Method and apparatus for treating acidic tail gas by using ammonia process flue gas |
US14/409,781 US20160030883A1 (en) | 2013-04-24 | 2013-04-24 | Method and apparatus for treating acidic tail gas by using ammonia process flue gas |
MX2015014913A MX358479B (es) | 2013-04-24 | 2013-04-24 | Metodo y aparato para tratar gas de cola acido al usar gas de combustible del proceso de amoniaco. |
PCT/CN2013/074657 WO2014172860A1 (zh) | 2013-04-24 | 2013-04-24 | 酸性尾气氨法烟气治理方法及装置 |
RS20180507A RS57661B1 (sr) | 2013-04-24 | 2013-04-24 | Postupak i aparatura za obradu kiselog otpadnog gasa upotrebom amonijačnog postupka |
EA201592029A EA029429B1 (ru) | 2013-04-24 | 2013-04-24 | Способ обработки топочного газа и устройство для обработки кислотных хвостовых газов с использованием аммиачного процесса |
PL13882863T PL2990096T3 (pl) | 2013-04-24 | 2013-04-24 | Sposób i urządzenie do oczyszczania kwaśnego gazu resztkowego z zastosowaniem procesu amoniakalnego |
ES13882863.7T ES2669735T3 (es) | 2013-04-24 | 2013-04-24 | Método y aparato para tratar gas de cola ácido usando el proceso con amoniaco |
HUE13882863A HUE039257T2 (hu) | 2013-04-24 | 2013-04-24 | Eljárás és berendezés savanyú véggáz ammónia-eljárás alkalmazásával történõ kezelésére |
EP13882863.7A EP2990096B1 (en) | 2013-04-24 | 2013-04-24 | Method and apparatus for treating acidic tail gas by using ammonia process |
BR112015027018-2A BR112015027018B1 (pt) | 2013-04-24 | 2013-04-24 | Método de tratamento de gás de combustão para tratar gás residual ácido utilizando um processo de amônia e aparelho de tratamento de gás de combustão para tratar gás residual ácido utilizando um processo de amônia |
US14/829,905 US9370745B2 (en) | 2013-04-24 | 2015-08-19 | Flue gas-treating method and apparatus for treating acidic tail gas by using ammonia process |
Applications Claiming Priority (1)
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PCT/CN2013/074657 WO2014172860A1 (zh) | 2013-04-24 | 2013-04-24 | 酸性尾气氨法烟气治理方法及装置 |
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US14/409,781 A-371-Of-International US20160030883A1 (en) | 2013-04-24 | 2013-04-24 | Method and apparatus for treating acidic tail gas by using ammonia process flue gas |
US14/829,905 Continuation US9370745B2 (en) | 2013-04-24 | 2015-08-19 | Flue gas-treating method and apparatus for treating acidic tail gas by using ammonia process |
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US (1) | US20160030883A1 (zh) |
EP (1) | EP2990096B1 (zh) |
BR (1) | BR112015027018B1 (zh) |
CA (1) | CA2908484C (zh) |
EA (1) | EA029429B1 (zh) |
ES (1) | ES2669735T3 (zh) |
HU (1) | HUE039257T2 (zh) |
MX (1) | MX358479B (zh) |
PL (1) | PL2990096T3 (zh) |
RS (1) | RS57661B1 (zh) |
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- 2013-04-24 HU HUE13882863A patent/HUE039257T2/hu unknown
- 2013-04-24 US US14/409,781 patent/US20160030883A1/en not_active Abandoned
- 2013-04-24 RS RS20180507A patent/RS57661B1/sr unknown
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CN110856797A (zh) * | 2018-08-22 | 2020-03-03 | 江苏凯亚环保科技有限公司 | 一种环保型氨法脱硫系统 |
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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MX2015014913A (es) | 2016-06-02 |
CA2908484C (en) | 2019-09-24 |
RS57661B1 (sr) | 2018-11-30 |
BR112015027018A2 (pt) | 2017-07-25 |
US20160030883A1 (en) | 2016-02-04 |
EP2990096A1 (en) | 2016-03-02 |
CA2908484A1 (en) | 2014-10-30 |
PL2990096T3 (pl) | 2018-09-28 |
HUE039257T2 (hu) | 2018-12-28 |
EA029429B1 (ru) | 2018-03-30 |
EA201592029A1 (ru) | 2016-02-29 |
MX358479B (es) | 2018-08-22 |
EP2990096A4 (en) | 2016-04-13 |
EP2990096B1 (en) | 2018-03-21 |
BR112015027018B1 (pt) | 2019-06-04 |
ES2669735T3 (es) | 2018-05-29 |
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