WO2019062451A1 - Agent de désulfuration de gaz de combustion, son procédé de production et son application - Google Patents

Agent de désulfuration de gaz de combustion, son procédé de production et son application Download PDF

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Publication number
WO2019062451A1
WO2019062451A1 PCT/CN2018/103028 CN2018103028W WO2019062451A1 WO 2019062451 A1 WO2019062451 A1 WO 2019062451A1 CN 2018103028 W CN2018103028 W CN 2018103028W WO 2019062451 A1 WO2019062451 A1 WO 2019062451A1
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parts
weight
nano
desulfurizing agent
sized
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PCT/CN2018/103028
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English (en)
Chinese (zh)
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童裳慧
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中晶环境科技股份有限公司
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Publication of WO2019062451A1 publication Critical patent/WO2019062451A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium

Definitions

  • the invention relates to a flue gas desulfurizing agent and a production method and application thereof, in particular to a dry desulfurizing agent, a production method thereof and a flue gas dry desulfurization method.
  • the current desulfurization methods are roughly classified into three categories: (1) wet method, washing with a liquid absorbent (such as water or an alkali solution, etc.); (2) semi-dry method, utilizing flue gas sensible heat to evaporate water in the lime slurry while lime Reacts with SO 2 to form dry powdered calcium sulfite, which combines the characteristics of wet and dry methods; (3) dry method, using powdery or granular absorbent, adsorbent or catalyst to remove SO 2 .
  • the wet desulfurization technology is relatively mature, and it has been used for decades in commercial application, but there are problems such as high freight rate, large water consumption, and secondary pollution caused by by-products.
  • the dry and semi-dry methods have the advantages of low cost, simple process, convenient maintenance, wide range of desulfurization efficiency, reliable operation and strong adaptability, and have attracted widespread attention.
  • the semi-dry method does not fundamentally solve the problem of renewable resources.
  • the dry desulfurization process is mostly a gas-solid reaction, the speed is relatively low, the reaction time of the flue gas in the reactor is long, the flue gas after desulfurization does not cool down, and heating is not required, so that the discharge diffusion requirement can be met.
  • the dry desulfurization technology has the advantages of no scaling, condensation, blockage, high reliability, and less secondary pollution.
  • the commonly used dry desulfurizers are mainly activated carbon or activated coke.
  • Desulfurization with activated carbon is a cost-effective method for desulfurization. Due to the low desulfurization temperature of activated carbon and simple operation, the produced sulfuric acid can also be recycled as a by-product. Therefore, desulfurization with activated carbon is a promising desulfurization method.
  • Chinese Patent Application No. 99104245.X discloses a method for preparing a desulfurizing agent by using activated carbon or activated carbon fiber as a carrier to support copper oxide. However, since the carbon material has low strength, high abrasion, few cycles of recycling, and high production cost.
  • the active coke of commercial scale application also has problems of low desulfurization capacity, frequent regeneration, and large usage. Therefore, it is very necessary to develop a low-cost, high-activity dry desulfurizer to improve desulfurization performance, reduce usage, and reduce investment and operating costs.
  • Another object of the present invention is to provide a method for producing a desulfurizing agent which is simple in process and low in cost.
  • the present invention achieves the above object by the following technical solutions.
  • the invention provides a flue gas desulfurizing agent, which comprises the following components based on 100 parts by weight of a desulfurizing agent:
  • the desulfurizing agent preferably, based on 100 parts by weight of the desulfurizing agent, the desulfurizing agent comprises the following components:
  • the desulfurizing agent preferably, based on 100 parts by weight of the desulfurizing agent, the desulfurizing agent comprises the following components:
  • MgO is composed of micron-sized magnesium oxide and nano-sized magnesium oxide, and nano-scale magnesium oxide is 10 to 20 parts by weight;
  • CaO is composed of micron-sized calcium oxide and nano-sized calcium oxide, and nanometer.
  • Calcium oxide is 0.5 to 2 parts by weight; SiO 2 is composed of micron-sized silica and nano-sized silica, and nano-sized silica is 2 to 5 parts by weight; V 2 O 5 includes nano-sized vanadium pentoxide And the nano-sized vanadium pentoxide is 0.15-0.5 parts by weight; the CeO 2 is composed of micron-sized ceria and nano-sized ceria, and the nano-sized ceria is 0.1-0.3 parts by weight; the Al 2 O 3 includes nano-n The grade of aluminum oxide, and the nanometer aluminum oxide is 0.15 to 0.5 parts by weight; and the MnO 2 comprises nanometer manganese dioxide, and the nanometer manganese dioxide is 5 to 8 parts by weight.
  • the nanometer magnesium oxide is 15 to 20 parts by weight; the nano-sized calcium oxide is 1 to 2 parts by weight; the nano-sized silica is 3 to 5 parts by weight; and the nano-sized vanadium pentoxide is used. It is 0.2 to 0.3 parts by weight; the nano-sized cerium oxide is 0.15 to 0.2 parts by weight; the nano-sized aluminum oxide is 0.2 to 0.3 parts by weight; and the nano-sized manganese dioxide is 6 to 7 parts by weight.
  • the active magnesium oxide content in MgO is 50 to 75 wt%.
  • the active magnesium oxide content in MgO is 62 to 75 wt%.
  • the desulfurizing agent is a flue gas dry desulfurizing agent.
  • the present invention also provides a method of producing a desulfurizing agent comprising the step of uniformly mixing the components.
  • the invention also provides a method for dry desulfurization of flue gas, wherein the desulfurizing agent is formed into a dry powder form, and then fully contacted with the flue gas for more than 30 minutes, thereby removing sulfur dioxide in the flue gas; wherein the flue gas has a sulfur dioxide content of 1000 ⁇ 3000 mg/Nm 3 , a flow rate of 2 to 5 m/s, and a temperature of 105 to 160 ° C.
  • the invention combines magnesium oxide with a metal oxide and an inorganic non-metal oxide organically to form a flue gas desulfurizing agent with high desulfurization efficiency.
  • a suitable amount of nano-sized metal oxides and inorganic non-metal oxides can further enhance the flue gas desulfurization effect.
  • the desulfurizing agent of the present invention includes magnesium oxide and a modifier.
  • Magnesium oxide includes light burned magnesia, micron-sized magnesia, and nano-sized magnesia.
  • Modifiers include micron and nanoscale metal oxides and inorganic non-metal oxides.
  • Metal oxides include nano- and micro-scale calcium oxide, aluminum oxide, manganese dioxide, vanadium pentoxide, and cerium oxide.
  • Inorganic non-metal oxides include nano-scale and micro-scale silica. The present inventors have found that combining these modifiers with magnesium oxide can significantly improve the flue gas desulfurization effect.
  • V 2 O 5 is decomposed into oxygen and vanadium pentoxide at a high temperature, and SO 2 is catalytically oxidized to SO 3 by the decomposition of oxygen. Subsequent elementary reactions are the absorption of oxygen in the gas phase to supplement the oxygen that has been incorporated into the reaction. V 2 O 5 reduces the activation energy of the reaction process in which SO 2 is oxidized to SO 3 , thereby accelerating the reaction rate. The SO 3 is further reacted with magnesium oxide to form a sulfate to achieve a desulfurization effect.
  • MgO is 70 to 90 parts by weight, preferably 80 to 90 parts by weight, and more preferably 85 to 88 parts by weight.
  • the active magnesium oxide content in the MgO may be from 50 to 75 wt%, preferably from 62 to 75 wt%, more preferably from 65 to 70 wt%. This is beneficial to improve its absorption of sulfur trioxide, thereby improving the desulfurization effect.
  • the MgO may be composed of micron-sized magnesium oxide and nano-sized magnesium oxide, and the nano-sized magnesium oxide is 10 to 20 parts by weight; preferably 15 to 20 parts by weight. This can further improve the desulfurization effect.
  • CaO is from 0.5 to 4 parts by weight, preferably from 0.8 to 3 parts by weight, more preferably from 2 to 3 parts by weight.
  • CaO is composed of micron-sized calcium oxide and nano-sized calcium oxide, and the nano-sized calcium oxide is 0.5 to 2 parts by weight; preferably 1 to 2 parts by weight.
  • Calcium oxide can assist in the absorption of sulfur trioxide, thereby improving the desulfurization effect.
  • SiO 2 is 2 to 10 parts by weight, preferably 3 to 8.5 parts by weight, and more preferably 5 to 8 parts by weight.
  • SiO 2 is composed of micron-sized silica and nano-sized silica, and the nano-sized silica is 2 to 5 parts by weight; preferably 3 to 5 parts by weight.
  • Silica promotes the catalytic effect and thereby improves the desulfurization effect.
  • V 2 O 5 is 0.15 to 0.6 part by weight, preferably 0.2 to 0.4 part by weight, more preferably 0.35 to 0.4 part by weight.
  • V 2 O 5 includes nano-sized vanadium pentoxide, and the nano-sized vanadium pentoxide is 0.15 to 0.5 parts by weight; preferably 0.2 to 0.3 parts by weight.
  • CeO 2 is 0.1 to 0.4 part by weight, preferably 0.15 to 0.3 part by weight, more preferably 0.2 to 0.3 part by weight.
  • CeO 2 is composed of micron-sized ceria and nano-sized ceria, and the nano-sized ceria is 0.1 to 0.3 parts by weight; preferably 0.15 to 0.2 parts by weight.
  • Al 2 O 3 is 0.15 to 0.6 part by weight, preferably 0.2 to 0.4 part by weight, more preferably 0.2 to 0.3 part by weight.
  • the Al 2 O 3 includes nano-sized aluminum oxide, and the nano-sized aluminum oxide is 0.15 to 0.5 parts by weight; preferably 0.2 to 0.3 parts by weight.
  • Al2O3 can improve the catalytic effect and thus improve the desulfurization efficiency.
  • MnO 2 is 5 to 10 parts by weight, preferably 6 to 9 parts by weight, and more preferably 6 to 7 parts by weight.
  • MnO 2 includes nano-sized manganese dioxide, and the nano-sized manganese dioxide is 5 to 8 parts by weight; preferably 6 to 7 parts by weight.
  • the desulfurizing agent is a flue gas dry desulfurizing agent.
  • Dry flue gas desulfurization is also called dry flue gas desulfurization, which means that the flue gas is desulfurized without using slurry.
  • the dry flue gas desulfurization of the present invention is different from wet flue gas desulfurization, which does not require the use of a large amount of slurry, thereby avoiding the production of a large amount of industrial waste liquid.
  • the production method of the desulfurizing agent of the present invention comprises the step of uniformly mixing the above respective components.
  • magnesium oxide, calcium oxide, aluminum oxide, manganese dioxide, vanadium pentoxide, cerium oxide, and silicon dioxide are uniformly mixed to obtain a dry powdery desulfurizing agent.
  • the method of the present invention comprises a flue gas desulfurization step of forming the above desulfurizing agent into a dry powder form and then sufficiently contacting the flue gas (for example, pre-dusting flue gas) for more than 30 minutes to remove sulfur dioxide in the flue gas.
  • the flue gas has a sulfur dioxide content of 1000 to 3000 mg/Nm 3 , a flow rate of 2 to 5 m/s, and a temperature of 105 to 160 °C.
  • a pre-dusting step is preferably included: pre-dusting the flue gas to remove most of the dust particles to form a pre-dusting flue gas.
  • the above steps can be carried out in a pre-dusting device, the specific structure of which can be those well known in the art, such as an electrostatic precipitator.
  • the pre-dusting efficiency of the present invention may be 90% or more, preferably 95% or more. This can reduce the load of the subsequent process and improve the operational stability of the desulfurization.
  • the sulfur dioxide may have a sulfur dioxide content of from 1,000 to 3,000 mg/Nm 3 , preferably from 1,500 to 2,800 mg/Nm 3 , more preferably from 1,600 to 2,600 mg/Nm 3 .
  • the oxygen content may be 10 to 25 vol%, preferably 15 to 20 vol%.
  • the temperature may be from 105 to 160 ° C; preferably from 120 to 135 ° C.
  • the flow rate of the flue gas may be 2 to 5 m/s, preferably 2.5 to 3.5 m/s.
  • the above flue gas parameters all indicate the parameters at the flue gas inlet; the parameters at the flue gas outlet are determined according to the actual desulfurization conditions. The use of the above process parameters is beneficial to improve the desulfurization efficiency.
  • the flue gas desulfurization step of the present invention can be carried out in a desulfurization unit.
  • the desulfurization device can be a circulating fluidized bed absorption tower, so that the desulfurization agent can be sufficiently contacted with the pre-dusting flue gas to improve the desulfurization effect.
  • the contact time of the desulfurizing agent with the pre-dusting flue gas may be 30 min or more, for example, 30 to 60 min, preferably 35 to 50 min. This can balance the desulfurization effect and the flue gas treatment efficiency.
  • the dry powder of the desulfurizing agent and the pre-dusting flue gas are thoroughly mixed in the flue gas pipeline, and then enter the absorption tower for desulfurization treatment, and the flue gas after the desulfurization is discharged by the chimney.
  • a dust removing step may be further included: separating the desulfurized flue gas in a bag dust removing device to obtain purified flue gas and powdery by-products.
  • the components were uniformly mixed according to the formulation of Table 1, to obtain a desulfurizing agent D1.
  • the desulfurization agent was used for dry desulfurization, and the flow rate of the flue gas was 2.5 m/s; other parameters of the flue gas inlet and the parameters of the flue gas outlet are shown in Tables 2 and 3.
  • the concentration of sulfur dioxide in the purified flue gas is 45 mg/Nm 3 , and the desulfurization efficiency is 99.03%.
  • the components were uniformly mixed according to the formulation of Table 4 to obtain a desulfurizing agent D2.
  • the desulfurization agent is used for dry desulfurization, and the concentration of sulfur dioxide in the flue gas after purification is 27 mg/Nm 3 , and the desulfurization efficiency is 99.42%.
  • the parameters of the flue gas inlet are the same as those in the first embodiment, and the parameters of the flue gas outlet are shown in Table 5.
  • Serial number project Quantity unit 1 Export smoke volume (working conditions) 812434 m 3 /h 2 exhaust temperature 63 °C 3 Sulfur dioxide emission concentration 27 Mg/Nm 3 4 Desulfurization efficiency 99.42 % 5 Output of by-products 36.96 t/h
  • the components were uniformly mixed according to the formulation of Table 6, to obtain a desulfurizing agent D3.
  • the desulfurization agent is used for dry desulfurization, and the concentration of sulfur dioxide in the flue gas after purification is 15 mg/Nm 3 , and the desulfurization efficiency is 99.68%.
  • the parameters of the flue gas inlet are the same as those in the first embodiment, and the parameters of the flue gas outlet are shown in Table 7.
  • Serial number project Quantity unit 1 Export smoke volume (working conditions) 808579 m 3 /h 2 exhaust temperature 64 °C 3 Sulfur dioxide emission concentration 15 Mg/Nm 3 4 Desulfurization efficiency 99.68 % 5 Output of by-products 37.07 t/h

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
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Abstract

Un agent de désulfuration de gaz de combustion, son procédé de production et son application. Sur la base de 100 parties en poids de l'agent de désulfuration, l'agent de désulfuration comprend les composants suivants, en poids : de 70 à 90 parties de MgO, de 0,5 à 4 parties de CaO, de 2 à 10 parties de SiO2, de 0,15 à 0,6 partie de V2O5, de 0,1 à 0,4 partie de CeO2, de 0,15 à 0,6 partie d'Al2O3, et de 5 à 10 parties de MnO2.
PCT/CN2018/103028 2017-09-30 2018-08-29 Agent de désulfuration de gaz de combustion, son procédé de production et son application WO2019062451A1 (fr)

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CN201710918985.XA CN107441932A (zh) 2017-09-30 2017-09-30 烟气脱硫剂及其生产方法和应用
CN201710918985.X 2017-09-30

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Publication number Priority date Publication date Assignee Title
CN107441932A (zh) * 2017-09-30 2017-12-08 中晶蓝实业有限公司 烟气脱硫剂及其生产方法和应用
CN108404651B (zh) * 2018-02-01 2021-04-30 中海油天津化工研究设计院有限公司 一种用于新型干法水泥窑烟气催化脱硫的脱硫剂
CN109012075A (zh) * 2018-08-24 2018-12-18 中惠科银河北科技发展有限公司 一种烟气干法脱硫用脱硫剂及其制备方法
CN112403254B (zh) * 2020-11-20 2022-09-27 中国铝业股份有限公司 一种以赤泥为原料制备脱硫剂的方法及其制得的脱硫剂

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JPH02245222A (ja) * 1989-01-19 1990-10-01 Inst Fr Petrole 再生可能な吸収物質による循環流動床でのガス流出物の脱硫方法
WO2005051508A2 (fr) * 2003-11-19 2005-06-09 Toll Processing And Consulting, Llc Sorption d'oxyde(s) de soufre par contact avec des solides en couche du type chlorite
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CN107456865A (zh) * 2017-09-30 2017-12-12 中晶蓝实业有限公司 烟气脱硫脱硝的方法
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CN107551808A (zh) * 2017-09-30 2018-01-09 中晶蓝实业有限公司 烟气脱硫的方法

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